Durham E-Theses
Some reactions of tetrasulphur tetranitride and
trithiazyl trichloride
Alange, G. G.
How to cite:
Alange, G. G. (1969)
Some reactions of tetrasulphur tetranitride and trithiazyl trichloride, Durham theses,
Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/8384/
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SOME REACTIONS OP TETRASULPHUR TETRANITRIDE
AND T R I T H I A Z Y L TRICHLORIDE
by
G.G. ALANGE
A t h e s i s submitted f o r t h e degree of Doctor o f Philosophy
in the University
o f Durham
A u g u s t 1969
TABLE OF CONTENTS
Page
INTRODUCTION
SULPHUR NITRIDES
(i)
The s u l p h u r n i t r i d e s
1
(ii)
Disulphur d i n i t r i d e
3
( i i i ) Tetrasulphur tetranitride
5
( a ) R e d u c t i o n and o x i d a t i o n o f S^N^
9
(b) Tetrasulphur t e t r a n i t r i d e adducts
11
( c ) R e a c t i o n s o f S^N^ i n p o l a r s o l v e n t s
13
( d ) Some o t h e r i m p o r t a n t r e a c t i o n s o f S^N^
14
(iv)
Polymeric sulphur n i t r i d e
16
(v)
Tetrasulphur d i n i t r i d e
(vi)
Polymeric sulphur n i t r i d e s ,
(SN)
x
17
S
N
1
5
a
n
d
2
S
N
i6 2
1
8
SULPHUR NITROGEN HALOGEN COMPOUNDS
(i)
(ii)
Monomeric t h i a z y l h a l i d e s
19
(a) Thiazyl
chloride
19
(b) T h i a z y l
fluoride
22
Polymeric t h i a z y l halides
24
( a ) P o l y t h i a z y l bromide
24
(b)
( i ) Trithiazyl trichloride
25
(ii) Trithiazyl trifluoride
29
(c) Tetrathiazyl
tetrafluoride
30
( i i i ) S u l p h u r n i t r o g e n h a l i d e s d e r i v e d from s u l p h u r
hexafluoride (Thiazyl t r i f l u o r i d e )
32
(iv)
T h i o d i t h i a z y l monochloride d i c h l o r i d e
34
(v)
Thiotrithiazyl halides
and d i f l u o r i d e
36
EXPERIMENTAL
PREPARATIONS
Tetrasulphur t e t r a n i t r i d e
40
Phenylboron d i c h l o r i d e
42
D i p h e n y l mercury
42
p-Tolytin trichloride
Metal
42
halides
( i ) T i n tetrabromide, t e t r a c h l o r i d e ,
and t e t r a i o d i d e
tetrafluoride
( i i ) Titanium tetrabromide, t e t r a c h l o r i d e ,
and
43
tetrafluoride
tetraiodide
( i i i ) Zirconium t e t r a c h l o r i d e
44
and t e t r a f l u o r i d e
44
(iv)
Hafnium t e t r a c h l o r i d e
44
(v)
A l u m i n i u m t r i b r o m i d e and t r i c h l o r i d e
44
(vi)
Gallium t r i c h l o r i d e
44
(vii)
Indium t r i c h l o r i d e
44
( v i i i ) Thallium t r i c h l o r i d e
44
(ix)
Selenium t e t r a c h l o r i d e
and t e t r a f l u o r i d e
(x)
Tellurium
(xi)
Niobium p e n t a c h l o r i d e and p e n t a f l u o r i d e
47
(xii)
T a n t a l u m p e n t a c h l o r i d e and p e n t a f l u o r i d e
47
t e t r a f l u o r i d e and t e t r a i o d i d e
( x i i i ) Vanadium o x y t r i c h l o r i d e
(xiv)
T u n g s t e n t e t r a b r o m i d e , t e t r a c h l o r i d e and
oxytetrachloride
Trithiazyl
trichloride
45
46-47
47
47
48
DRYING AND PURIFICATION OF SOLVENTS AND OTHER L I Q U I D
MATERIALS
Carhon t e t r a c h l o r i d e
49
Carbon d i s u l p h i d e
49
Methylene d i c h l o r i d e
50
Sulphuryl chloride
50
Thionyl chloride
50
Nitriles
50
Epoxides
50
Page
EXPERIMENTAL TECHNIQUES
The Drybox
50
M o l e c u l a r Weights
52
Mass S p e c t r a
53
Infrared
54
spectra
REACTIONS
R e a c t i o n between t e t r a s u l p h u r
(i)
(ii)
t e t r a n i t r i d e and m e t a l
T i n tetrabromide, t e t r a c h l o r i d e ,
tetraiodide
Germanium
t e t r a f l u o r i d e and
52-55
tetrachloride
56
( i i i ) Silicon tetrachloride
56
(iv)
Selenium t e t r a c h l o r i d e
(v)
Tellurium tetrachloride,
tetraiodide
(vi)
(vii)
T i t a n i u m tetrab.romide,
halides:
56-57
t e t r a f l u o r i d e and
57-58
tetrachloride,
t e t r a f l u o r i d e and t e t r a i o d i d e
58-60
Z i r c o n i u m t e t r a c h l o r i d e and t e t r a f l u o r i d e
60-61
( v i i i ) Hafnium t e t r a c h l o r i d e
61
(ix)
Antimony p e n t a c h l o r i d e and p e n t a f l u o r i d e
61-62
(x)
Niobium p e n t a c h l o r i d e and p e n t a f l u o r i d e
62-63
(xi)
T a n t a l u m p e n t a c h l o r i d e and p e n t a f l u o r i d e
62-63
(xii)
Tungsten tetrabromide, t e t r a c h l o r i d e
and
oxytetrachloride
64
( x i i i ) Vanadium o x y t r i c h l o r i d e
65
(xiv)
Aluminium t r i b r o m i d e and t r i c h l o r i d e
(xv)
Gallium t r i c h l o r i d e
66
(xvi)
Indium t r i c h l o r i d e
67
( x v i i )T h a l l i u m t r i c h l o r i d e
(xviii)
67-68
Iron t r i c h l o r i d e
R e a c t i o n between t e t r a s u l p h u r
68
t e t r a n i t r i d e and
Phenylboron d i c h l o r i d e
R e a c t i o n between t e t r a s u l p h u r
Tolytin trichlotide
65-66
69
t e t r a n i t r i d e and p69
Page
R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e
and
t r i m e t h y l aluminium
70
R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e
and
phenylmercuric c h l o r i d e
70
R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e
and
sulphuryl chloride
70
R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e
and c h l o r i n e
71
R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e and bromine
73
R e a c t i o n between t r i t h i a z y l
73
Reactions of t r i t h i a z y l
t r i c h l o r i d e and bromine
trichloride
( i ) R e a c t i o n between t r i t h i a z y l
t r i c h l o r i d e and c h l o r i n e
( i i ) Attempted p r e p a r a t i o n of S^N^Cl^
74
74
( i i i ) Attempted o x i d a t i o n of S^N^Cl^
( a ) Attempted o x i d a t i o n of t r i t h i a z y l
using S e 0
(b) Attempted o x i d a t i o n of t r i t h i a z y l
u s i n g l2°5
trichloride
75
2
( c ) Attempted o x i d a t i o n of t r i t h i a z y l
trichloride
7
trichloride
u s i n g ozone
76
(iv)
R e a c t i o n between t r i t h i a z y l
t r i c h l o r i d e and p y r i d i n e
(v)
R e a c t i o n between t r i t h i a z y l
d i p h e n y l mercury
trichloride
and
(vi)
R e a c t i o n between t r i t h i a z y l t r i c h l o r i d e
antimony t r i c h l o r i d e i n SOClg
and
( v i i ) R e a c t i o n between t r i t h i a z y l t r i c h l o r i d e
t i t a n i u m t e t r a c h l o r i d e i n SOClg
and
76-77
77-78
78
( v i i i ) R e a c t i o n between t r i t h i a z y l
p e n t a c h l o r i d e i n S0C1
t r i c h l o r i d e and antimony
(ix)
t r i c h l o r i d e and e p o x i d e s
R e a c t i o n between t r i t h i a z y l
5
79
79
(a) Epichlorohydrin
79
(b) Epibromohydrin
80
( c ) E t h y l e n e oxide
81
(d) Butylene
81
oxide
(x)
R e a c t i o n between t r i t h i a z y l
phenyl a c e t y l e n e
t r i c h l o r i d e and
(xi)
R e a c t i o n between t r i t h i a z y l
diphenyl acetylene
t r i c h l o r i d e and
( x i i ) R e a c t i o n between t r i t h i a z y l
monoxide
t r i c h l o r i d e and c a r b o n
( x i i i ) Reaction
t r i c h l o r i d e and n i t r i l e s
between t r i t h i a z y l
(a)
Acetonitrile
(b)
Propionitrile
(c)
Isobutyronitrile
(d) T e t t i a r y b u t y l
cyanide
(e)
Benzonitrile
(f)
Trichloroacetonitrile
DISCUSSION
Tetrasulphur t e t r a n i t r i d e
adducts w i t h Lewis
acids
(a) Tetrasulphur t e t r a n i t r i d e adducts o f t i n
t e t r a b r o m i d e and t e t r a c h l o r i d e
(b) T e t r a s u l p h u r t e t r a n i t r i d e adducts of t i t a n i u m ,
z i r c o n i u m and h a f n i u m t e t r a h a l i d e s
( c ) T e t r a s u l p h u r t e t r a n i t r i d e a d d u c t s o f boron,
a l u m i n i u m , g a l l i u m , i n d i u m , t h a l l i u m and i r o n
trihalides
( d ) T e t r a s u l p h u r t e t r a n i t r i d e adducts o f antimony,
n i o b i u m and t a n t a l u m h a l i d e s
( e ) T e t r a s u l p h u r t e t r a n i t r i d e adducts of selenium
( I V ) , t e l l u r i u m ( I V ) and t u n g s t e n h a l i d e s and
oxyhalides
The s t r u c t u r e s
o f S„N. a d d u c t s
4 4
( a ) The s t r u c t u r e s
of S n B r
4 >
2S N
4
( b ) The s t r u c t u r e s o f S N . 4 T i F
S.N^.ZrCl,, and S.N^.HfCl,,
4 4
4
4 4
4
4
( c ) The s t r u c t u r e s
4
and S n C l . 2 S N
4
, S N
4
4
5
4
.TiBr ,
4
of S N . S b C l , S N .4SbF ,
4
4
&
4
S N .NbCl , S N .NbF , S N . T a C l
4
4
4
4
5
4
4
4
5
5
and S ^ . T a F g
Page
(d)
The s t r u c t u r e s o f S N . 2 A l C l , S N . 2 A l B r
4
4
3
4
4
3
S N .2GaCl , S N . 2 I n C l , S N .2T1C1 ,
4
4
3
4
4
3
4
4
3
S..N,, .2FeCl„ a n d S N .PhBCl_
4 4
3
4 4
2
/1
(e)
130
yl
The s t r u c t u r e s o f S . N - . T e C l . and S . N - . S e C l .
4 4
(f)
4
4
4
The s t r u c t u r e s o f S N .WBr , S N .WC1 ,
4
4
4
4
4
S N .W0C1 (?)
The p r e p a r a t i o n and r e a c t i o n s o f t r i t h i a z y l
4
(a)
4
132
4
4
4
trichloride
134
136
Attempted p r e p a r a t i o n of s u l p h a n u r i c c h l o r i d e
from t r i t h i a z y l t r i c h l o r i d e
142
R e a c t i o n between t r i t h i a z y l t r i c h l o r i d e and
d i p h e n y l mercury and p y r i d i n e
143
Reaction of t r i t h i a z y l t r i c h l o r i d e with
epibromohydrin , e p i c h l o r o h y d r i n , ethylene
o x i d e and b u t y l e n e o x i d e
144
R e a c t i o n between t r i t h i a z y l
nitriles
146
(b)
(c)
(d)
APPENDIX
REFERENCES
t r i c h l o r i d e and
154
156
SUMMARY
The
(a)
t h e s i s c a n be
conveniently
the r e a c t i o n s of t e t r a s u l p h u r
r e a c t i o n s of t r i t h i a z y l
(a) Reactions
The
t e t r a n i t r i d e and
r e a c t i o n s of t e t r a s u l p h u r
t e t r a n i t r i d e w i t h many
t h a t i n most o f t h e s e
of S^N^ i s c o o r d i n a t e d
Adducts
have
compounds
to the Lewis a c i d .
The
the
following
compounds h a v e been p r e p a r e d : 2 S N . S n B r ^ , S ^ N ^ . T i B r ^ ,
4
N
-
4
4 T i F
4'
S
N
4
4-
T i I
4'
S
N
4
4'
Z r C 1
4» 4
V
4
HfC1
S N
4
' -
4
4
4
4
4
T a F , S N .2A1C1 , S N .2AlBr , S ^ ^ G a C l g ,
5
4
4
3
4
4
SeC1
4 4
S N . T e C l , S N .TeF , S^.NbCl,., S ^ . N b F ^
4
the
s o l v e n t s h a v e been s t u d i e d .
S
4
(b)
(S^N^: L e w i s a c i d ) s t d b h i o m e t r y
been p r e p a r e d ; i t i s l i k e l y
S
parts
of t e t r a s u l p h u r t e t r a n i t r i d e
o f 2:1, 1 : 1 j 1:2, 1:4
new
i n t o two
trichloride.
1 Lewis a c i d s i n i n e r t organic
nitrogen
divided
3
4
»
S^.TaCl,.,
S ^ .
S N .2lnCl ,
4
4
3
S N . 2 T 1 C 1 ( ? ) , S N . P h B C l , S N .WBr , S ^ . W O C l ^ ? ) .
4
4
3
Silicon
do not
gives
and
4
4
4
4
4
t e t r a c h l o r i d e , germanium t e t r a c h l o r i d e and
r e a c t under t h e c o n d i t i o n s
2S N .SnCl
4
4
4
due
studied;
to d i s p r o p o r t i o n
t i n tetraiodide
p-tolytin
trichloride
into t i n tetrachloride
tetra-p-tolytin.
The
i n f r a r e d s p e c t r a of t h e new
previously
reported
have been d i s c u s s e d .
two
2
types
a d d u c t s and
a d d u c t s a r e r e c o r d e d and
T h e s e compounds c a n
( i ) adducts with
some o f
their
the
structures
be r o u g h l y d i v i d e d
i n f r a r e d s p e c t r a s i m i l a r to the
into
infrared
of compounds o f known s t r u c t u r e
(S^N^.SbCij., S^N^.BFg) and
( i i ) t h e i n f r a r e d s p e c t r a o f p r o d u c t s whose s p e c t r a d i f f e r
infrared spectra of S N .SbCl
4
( i ) a r e considered
4
to contain
5
and S N . B F g .
4
monodentate S N ; i n o t h e r
p o s s i b l e s t r u c t u r e s have been d i s c u s s e d
adducts described
4
by a n a l o g y w i t h
4
c h l o r i d e and ( b ) c h l o r i n e
trichloride
4
synthesis
and ( b ) a new compound t h o u g h t t o be
trichloride
The s e c o n d p a r t o f t h e t h e s i s d e a l s w i t h
reactions.
no o t h e r r e a c t i o n s
o f t h i s compound a r e known.
the following
(NSOC H BrCl) , ( i i i ) (NSOC^CDg,
3
5
3
Trithiazyl trichloride
trithiazyl
A p a r t from c o n v e r s i o n t o t h e t r i f l u o r i d e
r e a c t s with epoxides t o give
(ii)
other
and ( a ) s u l p h u r y 1
l e d t o ( a ) a new c o n v e n i e n t
(b) Reactions of t r i t h i a z y l
trichloride
cases
i n the l i t e r a t u r e .
A s t u d y o f t h e r e a c t i o n s between S N
for t r i t h i a z y l
Compounds o f t y p e
4
4
from t h e
Trithiazyl
e s t e r s ( i ) (NSO.CgHgClg)^
( i v ) (NS0C H 0)g.
4
reactions with n i t r i l e s yielded
of p r o d u c t s and p o s s i b l e
trichloride
structures are discussed.
g
a variety
ACKNOWLEDGEMENTS
The
to
author wishes
thanks
D r . A . J . B a n i s t e r under whose g u i d a n c e t h i s r e s e a r c h
was c a r r i e d
o u t , f o r h i s h e l p , v a l u a b l e a d v i c e and c o n s t a n t
encouragement
are
to express h i s g r a t e f u l
throughout t h e c o u r s e o f t h e work.
Thanks
due t o S.C.S. C o l l e g e Omerga, D r . N . K . H a z a r i and M r s .
P. B l a i r
o f Durham
f o r t h e i r h e l p i n many ways and t h e U n i v e r s i t y
for research
facilities.
-1-
INTRODUCTION
The c h e m i s t r y
o f s u l p h u r n i t r o g e n compounds h a s been
a t o p i c of i n t e r e s t
tetranitride.'''
since the f i r s t
s y n t h e s i s of t e t r a s u l p h u r
Today many s u l p h u r n i t r o g e n compounds a r e
known w h i c h a r e d e r i v e d from t h i s n i t r i d e and t h e i r
has been t h o r o u g h l y i n v e s t i g a t e d .
I t shows h a r d l y any a n a l o g y
w i t h t h a t o f n i t r o g e n oxygen compounds.
may be a s c r i b e d t o t h e f a c t s
chemistry
This observation
that ( a ) nitrogen i s the less
2
e l e c t r o n e g a t i v e p a r t n e r i n b i n a r y oxygen n i t r o g e n compounds ,
( b ) many o f t h e c h a r a c t e r i s t i c p r o p e r t i e s o f oxygen a r e r e l a t e d
to i t s s m a l l s i z e ,
thus i t s i o n i z a t i o n p o t e n t i a l
higher than f o r sulphur,
d-orbitals
limits
( c ) the n o n - a v a i l a b i l i t y
the covalency
maximum t o f o u r .
of s u l p h u r - n i t r o g e n compounds h a s s e v e r a l
i m p o r t a n t f e a t u r e s , namely, s t a b i l i t y
i s appreciably
t o oxygen o f
The c h e m i s t r y
i n t e r e s t i n g and
o f t h e s u l p h u r - n i t r o g e n bond,
t e n d e n c y t o form s i x and e i g h t membered r i n g s , r i n g c o n t r a c t i o n ,
p o l y m e r i s a t i o n and i o n f o r m a t i o n .
Compounds w i t h s i x o r e i g h t
membered r i n g s o f a l t e r n a t i n g s u l p h u r - n i t r o g e n atoms have
considerable interest
of t h e i r
The s u l p h u r
i n connection with
3 4 5
TT-electrons
aroused
t h e bonding p r o p e r t i e s
' ' .
nitrides
1
Monomeric s u l p h u r n i t r i d e o r ' t h i a z y l ,
SN i s t h e t h i o 5
analogue of n i t r i c
o x i d e , and l i k e n i t r i c
oxide,
i s a radical
.
-2-
Nitric
o x i d e e x h i b i t s a tendency t o l o s e e l e c t r o n s t o form
p o s i t i v e l y charged
elemental
nitrosonium i o n which i s i s o e l e c t r o n i c
n i t r o g e n and
the cyanide
ion.
i s some e v i d e n c e
t h a t a p o s i t i v e S=N s p e c i e s does e x i s t a s an
especially since trithiazyl
trichloride,
lower
t h e r e would a p p e a r
t o be a g r e a t e r t e n d e n c y t o form a c a t i o n but no d e f i n i t e
There
with
Because of the
e l e c t r o n e g a t i v i t y o f s u l p h u r compared w i t h 0,
compounds have been i s o l a t e d .
the
NS
however,
intermediate,
(NSC1)_, i s obtained
7
by
t h e d i r e c t c h l o r i n a t i o n of ^ N ^ .
been d e t e c t e d
n i t r o g e n and
I t has o n l y
actually
(from i t s e m i s s i o n spectrum) i n a mixture
8
discharge .
s u l p h u r vapour s u b j e c t e d t o a n e l e c t r i c
I t h a s a l s o been p r e p a r e d
by
of
the r e a c t i o n of H S w i t h
atomic
9
nitrogen,
and
i t s presence
a s an i n t e r m e d i a t e i n r e a c t i o n s o f
some s u l p h u r - n i t r o g e n compounds has been i n v o k e d .
many r e a c t i o n s of t r i t h i a z y l
proceed
by way
trichloride,
Since
(NSC1) , i n s o l u t i o n
1
of t h i a z y l c h l o r i d e , N S C l * , s e v e r a l r e a c t i o n s
of t e t r a s u l p h u r t e t r a n i t r i d e may
proceed
v i a monomeric
sulphur
n i t r i d e NS.
The
s t r u c t u r e o f monomeric t h i o n i t r o s y l c a n be
by a t y p i c a l
nitric
oxide.
represented
3 - e l e c t r o n bond c o n f i g u r a t i o n , a s i n t h e c a s e
of
I n p r i n c i p l e a s t a b l e i o n c a n be a c h i e v e d by
loss
of an e l e c t r o n t o g i v e N=s", o r by e l e c t r o n a d d i t i o n t o g i v e N=S .
-3-
The
monomer, NS
c a n be r e p r e s e n t e d e i t h e r by a V.B. r e p r e s e n t a t i o n
i n v o l v i n g a t h r e e e l e c t r o n bond,
M.O.
:N=S:
p i c t u r e s i m i l a r to that for
The
probable
analogy
carbon
t h e C=N
groups i n
cyanogen compounds a p p e a r s
worthy of
S u c h t r i p l e bonds t o n i t r o g e n a r e s t a b l e among t h e
compounds R-C=N; t h e y a r e a p p a r e n t l y not s t a b l e i n
phosphorus c h e m i s t r y
f o r N S F , NSF
3
Disulphur
and
(N=PX3) and
a r e o n l y knowfr i n s u l p h u r
dinitride
vapour l e d t h r o u g h
t o 300°C
chemistry
NSC1.
When t e t r a s u l p h u r t e t r a n i t r i d e i s s u b l i m e d
and
a
NO.
between an S^N and
t h e monomeric t h i a z y l and
consideration.
o r more p r e c i s e l y by
thermal
a little
i n vacuo and
a zone f i l l e d w i t h s i l v e r y wool and
f i s s i o n of t h e m o l e c u l e
s u l p h u r ( a s Ag^S) and
predominant product
occurs.
heated
Although
(SN)
n i t r o g e n a r e formed, t h e
(60% y i e l d ) c o n s i s t s of a white
volatile
Q
12
s u b s t a n c e w h i c h c a n be condensed i n a t r a p c o o l e d t o -196
T h i s compound i s s o l u b l e i n b e n z e n e , efaer, c a r b o n
Q
1
- 80
C.
t e t r a h y d r o f u r a n , d i o x a n e and c a n be r e c r y s t a l l i s e d
13 14
them, but i n s o l u b l e i n w a t e r
' .
The c o l o u r l e s s p r o d u c t
c o n t a i n s e q u a l numbers of s u l p h u r and
from
obtained
n i t r o g e n atoms
15
and
has t h e f o r m u l a S„N
0.01mm Hg
reported
12
.
I t s u b l i m e s a t room t e m p e r a t u r e
and h a s a s t r o n g u n p l e a s a n t odour.
?
tetrachloride,
acetone,
i n t h i s way
the
I t has
o
t o decompose e x p l o s i v e l y above 30 C o r on
been
impact.
at
-4-
I n more r e c e n t i n v e s t i g a t i o n s S N
v a p o u r was u n a f f e c t e d by g l a s s
wool a t 300° and on h e a t i n g above 30°, r a p i d p o l y m e r i s a t i o n n o t
17
d e t o n a t i o n was
observed
Disulphur d i n i t r i d e rapidly dimerises to tetrasulphur
t e t r a n i t r i d e when a n a l k a l i m e t a l o r a n a l k a l i c a r b o n a t e o r c y a n i d e
16
i s added t o i t s benzene s o l u t i o n .
Spontaneous p o l y m e r i s a t i o n
o
o c c u r s when t h e compound i s s t o r e d a t below 30 C.
with the composition
tetranitride.
(SN)
A compound
i s formed a s w e l l a s t h e t e t r a s u l p h u r
X
sulphur n i t r i d e (SN) i s the s o l e
13
product i f moisture i s r i g o r o u s l y excluded.
The i n f r a r e d s p e c t r u m and c h e m i c a l p r o p e r t i e s o f SgNg have
led
The p o l y m e r i c
X
t o i t s f o r m u l a t i o n a s a four-membered p l a n a r r i n g w i t h
alternating
14a
S and N atoms.
N
S
*
N
T h i s i s supported
S
by X - r a y
N
*
Nexamination
of t h e adduct S N
Ct
R e a c t i o n s o f d i s u l p h u r d i n i t r i d e w i t h antimony
.SbCl
&
17
0
pentachloride
17
and
b o r o n h a l i d e s h a v e been s t u d i e d r e c e n t l y
of donation
on t h e s t a b i l i t y
and t h e e f f e c t
and s t r u c t u r e o f t h e SgNg r i n g h a v e
been i n v e s t i g a t e d .
Solutions of S N
0
chloride
i n d i c h l o r o m e t h a n e r e a c t w i t h antimony
( i n e x c e s s ) and form a d i a d d u c t
penta-
S_N„(SbCl )„ w h i c h c a n
2. Z
o z
c
f u r t h e r r e a c t w i t h SgNg t o form a monoadduct SgNgSbClg.
The
-5-
monoadduct c a n be r e c o n v e r t e d t o t h e d i a d d u c t
SbCl,-•
5
by t r e a t m e n t
with
The p h y s i c a l and c h e m i c a l p r o p e r t i e s o f t h e s e compounds
i n d i c a t e that the S N
r i n g s t r u c t u r e i s maintained
intact.
The monoadduct SgNg.SbCIg r e a c t s i r r e v e r s i b l y w i t h S^Ng t o form
both t h e p r e v i o u s l y c h a r a c t e r i s e d S N .SbCl,- a n d , i n lower
4
4
a l e s s r e a c t i v e m a t e r i a l (S.N .SbCl,.) .
41 1
Antimony
yields,
pentachloride
OX
17
acts as a c a t a l y s t
f o r the dimerisation of S N ,
D i s u l p h u r d i n i t r i d e r e a c t s w i t h boron t r i c h l o r i d e i n
17
d i c h l o r o m e t h a n e t o form t h e f o l l o w i n g compounds:
S
N
4 4
B C 1
3'
S
N
2 2
( B C 1
)
3 2
a
n
d
(
S
2
N
B
2
C
1
3
)
2
-
l o s e s BC1„ t o form t h e a d d u c t S N BC1
the diadduct
by t r e a t m e n t
A
t
°°
C
S
N
2 2
( B C 1
)
3 2
w h i c h c a n be r e c o n v e r t e d t o
with BClg a t
-78°C.
Antimony
p e n t a c h l o r i d e SbCl,. d i s p l a c e s boron t r i c h l o r i d e ; B C l ^ from
S„N BC1
t o form S N ( S b C l - ) ,
is
toward b o t h B C l g and SbCl^..
0
inert
the polymeric
The p r o p e r t i e s o f SgNg
BC1„ and S N ( B C 1 „ ) . i n d i c a t e t h a t t h e S N
remains i n t a c t .
Tetrasulphur
compound, (S.N BC1„)
ring structure
R e a c t i o n o f SgNg w i t h B F ^ y i e l d s o n l y
S N BFg
4
17
4
tetranitride
The e a r l i e s t known n i t r i d e o f s u l p h u r i s t e t r a s u l p h u r
tetranitride.
The compound i s formed when d i s u l p h u r d i c h l o r i d e
and ammonia a r e r e a c t e d t o g e t h e r and was f i r s t
d i s c o v e r e d by
15
Gregory
.
T e t r a s u l p h u r t e t r a n i t r i d e c a n be formed i n a v a r i e t y
g
of r e a c t i o n s .
I t c a n a l s o be o b t a i n e d
from s e v e r a l o t h e r
sulphur-
-6-
n i t r o g e n compounds.
S^N^ i s u s u a l l y p r e p a r e d
g a s e o u s ammonia i n t o a s o l u t i o n o f s u l p h u r
i n an i n e r t
6SC1
s o l v e n t such a s C C l ^
+ 16NH
2
typical
•
3
dichloride, S C ^
16 18
'
(SjCl^
+ 2S + 12NH^Cl).
by p a s s i n g
+
C l
2 *
> S S S = S
2
S
C
l
2'
This preparation i s
f o r n o n - m e t a l - n i t r o g e n compounds ( v i z : non-metal h a l i d e
and NH^ o r NH^
+
salt).
I n organic
s o l v e n t s of low d i e l e c t r i c
c o n s t a n t y i e l d s o f S^N^ from d i s u l p h u r d i c h l o r i d e and ammonia a r e
higher
than i n s o l v e n t s o f high d i e l e c t r i c
constants.^
Insufficient
i s known about t h e c o u r s e o f t h e s u l p h u r - c h l o r i d e ammonia r e a c t i o n
t o be a b l e to e x p l a i n t h e s e y i e l d v a r i a t i o n s .
I t i s however,
thought
t h a t t h e t e t r a s u l p h u r t e t r a n i t r i d e may be formed v i a t h i o d i t h i a z y l
d i c h l o r i d e , S^i^Cl^,
c o n t a i n i n g a five-membered S-N r i n g and
t h i o t r i t h i a z y l c h l o r i d e S^N^Cl, w h i c h c o n t a i n s a s e v e n membered
6 21 22
ring.
'
'
A convenient
laboratory preparation f o r small
amounts o f t h e t e t r a n i t r i d e makes u s e o f t h e r e a c t i o n between
d i s u l p h u r d i c h l o r i d e v a p o u r and d r y p e l l e t s o f ammonium c h l o r i d e
a t 160°
(6S C1
2
2
+ 4NH C1
Tetrasulphur
4
•
+ 8S +
16HC1).
t e t r a n i t r i d e c a n a l s o be p r e p a r e d
2 3
by t h e
foUbwing methods:•i
(a)
Reaction
between e l e m e n t a l
t e m p e r a t u r e under p r e s s u r e .
sulphur
and l i q u i d ammonia a t room
While c r y s t a l l i n e sulphur
i s insoluble
i n t h i s medium below 11 '5°C, b l u e s o l u t i o n s a r e formed a t h i g h e r
t e m p e r a t u r e s w h i c h r e m a i n s t a b l e a t room t e m p e r a t u r e ( 1 0 S + 4NH^
-7-
6H
S + S N
the
I f H S i s removed f r o m / e q u i l i b r i u m
).
t e t r a s u l p h u r t e t r a n i t r i d e can be
.
a f t e r evaporating
S
from t h e s o l i d
12
by
t h e r e a c t i o n between d i s u l p h u r d i c h l o r i d e
l i t h i u m a z i d e i n an i n e r t s o l v e n t a t 0°C
24
(
2 V
+
4
L
i
C
1
;
2 S
2
2
( N
)
S
N
3 2~> 4 4
4
+
(4LiN
o r s u l p h u r compounds ( S
(d) I t i s obtained
by
+2S C1^—>2
0
V
( c ) I t i s formed when a c t i v e n i t r o g e n i s a l l o w e d
sulphur
residue
t h e ammonia
(b) I t i s prepared
and
isolated
system,
to r e a c t w i t h
(vapour)
> ^.N
t h e ammonolysis o f s u l p h u r
+ (NS)
) ^
tetrafluoride
NH
<
S F
4
— >
W
Tetrasulphur
s o l i d , m.p.
is
tetranitride
o 26
178 C
.
i n s o l u b l e i n water.
(moles per
0.23;
1000
i s a p a l e orange
I t d i s s o l v e s i n many o r g a n i c s o l v e n t s
27
I t has
the f o l l o w i n g
at 2 0 ° C ,
The
but
solubilities
g. s o l v e n t ) : d i o x a n e a t 18°C, 0.20,
carbon d i s u l p h i d e a t 0 ° C ,
benzene a t 0 ° C ,
crystalline
a t 60°C.,
0.0155, a t 3 0 ° C , 0.0573;
0.0137, a t 6 0 ° C , 0.121; e t h a n o l a t 0°C.,
0.0043,
0.0072.
molecular
s t r u c t u r e of t e t r a s u l p h u r t e t r a n i t r i d e ,
has been a s u b j e c t of c o n t r o v e r s y
which
f o r a l o n g p e r i o d o f t i m e i s now
28
29,30
established.
Electron diffraction
and X - r a y a n a l y s e s
, show
t h a t t h e S^N^ m o l e c u l e i s an e i g h t membered r i n g ( F i g . l ) .
I n the
28
29 30
vapour
and i n t h e s o l i d s t a t e ,
'
t h e t e t r a m e r i s i n t h e form o f
CD
o
if)
CM
GO
01
ro
<0
c8
00
GO
in
00
CM
V
CO
ro
in
V
ro
CNJ
-8-
o f a c r a d l e - t y p e p u c k e r e d r i n g w i t h a l l f o u r n i t r o g e n atoms
i n t h e same p l a n e .
A l l t h e s u l p h u r atoms a r e c h e m i c a l l y and
31
physically
identical
tetramer i s provided
.
Evidence
f o r pi-bonding i n the
by t h e f a c t t h a t
o 28,29
o f 1.62A
a r e s h o r t e r than
than
the c a l c u l a t e d
According
length
o
v a l u e o f 1.74A
the t h e o r e t i c a l
f o r S-N s i n g l e bonds, and l o n g e r
1.54/? f o r S=N d o u b l e bonds.
t h e e q u a l bond
value of
to the r e l a t i o n s h i p
I
32
l| | between S-N
bond o r d e r and t h e S-N
of 1.62A* c o r r e s p o n d s
plausibly
bond l e n g t h
, a bond
t o a bond o r d e r o f 1.5.
length
T h i s i s most
e x p l a i n e d by t h e e x i s t e n c e o f a p i - e l e c t r o n
system i n
the m o l e c u l e due t o o v e r l a p between t h e p - p i o r b i t a l o f n i t r o g e n
3 5
and t h e d - p i o r b i t a l o f s u l p h u r ' .
Self-consistent field
molecular o r b i t a l c a l c u l a t i o n s suggested that c o n s i d e r a b l e p i
,
electron
The
„
d e l o c a l i z a t i o n takes place in the (SN)^
calculations
u n i t s and t h a t
also indicate
33
system
t h a t bonds a r e p o l a r i s e d
some s u l p h u r - s u l p h u r
as % - §
bonding occurs mostly
by
o v e r l a p o f p o r b i t a l s , b u t o n e - t h i r d by o v e r l a p o f s u l p h u r d
xy
orbitals.
Electron
and
s p i n resonance
spectra
the spectrum of the anion,
(SN>
h a v e been o b s e r v e d
4
, was c o n s i s t e n t
34
u rc h n id te rl o gc ea nl i zatoms.
si tn rv uo cl tv ue rd e a il nl wf ho i
a t i o n occurred
over
with
with a
t h e r i n g and
(SN)^
-9-
The v i s i b l e and
interpreted
ultraviolet
spectra
of
(S-N)
h a v e been
4
i n t e r m s of a s t r u c t u r e i n w h i c h weak S-S
bonding
35
was
present
.
( a ) R e d u c t i o n and
The
oxidation
of
S.N.
4 4
h y d r o g e n a t i o n of t e t r a s u l p h u r
stannous c h l o r i d e
36
t e t r a n i t r i d e with
2-
or w i t h d i t h i o n i t e ,
produces
tetrasulphur
26
tetraimxde
the
.
T h i s has
not
been d e t e c t e d
s u l p h u r c h l o r i d e / a m m o n i a r e a c t i o n but
among t h e p r o d u c t s
may
w e l l be
of
there
i n very
minute q u a n t i t i e s .
T e t r a s u l p h u r t e t r a i m i d e was
6
d i s c o v e r e d by W o l b l i n g .
I t i s c o l o u r l e s s and c r y s t a l l i s e s i n
38
the orthorhombohedral system
39 40
The s t r u c t u r e o f S„N.H„ has been e l u c i d a t e d
' .
The
4 4 4
arrangement of the n i t r o g e n
crown s h a p e l i k e t h a t
sulphur nitrogen
and
i n the S
o
s u l p h u r atoms i n t h e
sulphur r i n g
bonds i n t e t r a s u l p h u r
40
'
41
tetraimide
3 9 40
- 1.67A
'
.
r i n g i s of
.
The
are equal i n
0
length
and
that there
are
i n t h e r a n g e 1.65
i s an a p p r e c i a b l e
This
amount of p i - c h a r a c t e r
implies
in
the
42
s k e l e t a l bonds, and
fact
.
that the r i n g s t r u c t u r e i s puckered suggests that
d o r b i t a l s are
by
t h a t some d e l o c a l i z a t i o n o c c u r s
involved,
donation of n i t r o g e n
and
pi-bonding probably
lone p a i r e l e c t r o n s
takes
to vacant
The
sulphur
place
sulphur
42
d orbitals
.
The d i a m a g n e t i c s u s c e p t i b i l i t y , however g i v e s
no e v i d e n c e o f any r i n g c u r r e n t a r i s i n g from d e l o c a l i z e d m u l t i p l e
•10-
G
bonding
43
'
, probably
v
because
donate i n t o s u l p h u r d o r b i t a l s ,
p l a n e s ) prevents the formation
' the n i t r o g e n lone p a i r s
will
t h e symmetry o f w h i c h (two
of u n i n t e r r u p t e d m o l e c u l a r
nodal
orbitals
42
e n c l o s i n g the whole molecule
( c f . chlorophosphazenes
).
The h y d r o g e n i n t e t r a s u l p h u r t e t r a i m i d e c a n be r e p l a c e d
44
by m e t a l s .
B e c k e - G o e h r i n g and S c h w a r z
o f S^N^ w i t h t r i p h e n y m e t h y l sodium and
s o l i d . Na.S„N„.
' 4
4 4
s t u d i e d the
obtained
reaction
orange-red
i s Na-(H„S .N . ) . w h i c h
2 2 4 4 '
44
been o b t a i n e d a s a lemon y e l l o w p r e c i p i t a t e
.
Stepwise
replacement
N
H
^4 4 4
a n c
*
by
n B u L i
-
A n o t h e r sodium s a l t
l i t h i u m has been o b s e r v e d
a n c l
t
n
e
51
has
1
i n the r e a c t i o n
between
v a r i o u s c o l o u r changes a r e r e d , y e l l o w ,
4-
blue, yellow.
The
i o n c o n t a i n e d i n t h e sodium
c a n be o b t a i n e d , r e d u c i n g S^N^ by o t h e r methods.
The
salts
reaction
o f t e t r a s u l p h u r t e t r a n i t r i d e w i t h sodium i n d i m e t h o x y e t h a n e shows
46
c o l o u r c h a n g e s , r e d , deep b l u e , g r e e n and y e l l o w g r e e n
.
When
S^N^ i s t r e a t e d w i t h v a c u u m - d i s t i l l e d p o t a s s i u m i n s c r u p u l o u s l y
46
dry d i m e t h o x y e t h a n e , v a r i o u s c o l o u r c h a n g e s a r e e x h i b i t e d
scarlet
red s o l u t i o n i s f i r s t
green s o l u t i o n i s produced.
observed,
The
on f u r t h e r s h a k i n g a
c o l o u r c h a n g e s h a v e been
i n t e r p r e t e d a s i n d i c a t i n g t h e f o r m a t i o n of t h e f o l l o w i n g
- .
46
sequence of ions
:
23444
44
44
44
red
yellow
b l u e or
blue-green
, a
yellow
or
yellow-green
-11-
Tetrasulphur tetraimicle
forms a d d u c t s ,
e . g . S^N^H^.
47
TeBr
S
N
H
i
s
A tetrameric thionylimide, (°4 4 4 4^
produced
48
from t h e a i r o x i d a t i o n o f S.N.H. .
F u r t h e r work on S„N„H„
4 4 4
4 4 4
is
.
4
i n progress
i n this
department.
(b) Tetrasulphur t e t r a n i t r i d e
adducts
In i n e r t organic solvents tetrasulphur t e t r a n i t r i d e
coloured
s t a b l e a d d u c t s w i t h many L e w i s
acids.
forms
The f o l l o w i n g
52,53
a d d u c t s have been p r e p a r e d
S
N
4 4'
B F
54
3 »
i n the past
: S^^SbCl^
50
4 S
N
4 4*
B F
3
( t h i s unusual stoLchbmetry i s probably
54
52 53
52 53
t o incomplete r e a c t i o n ) 2S.N..SnCl.
'
, S.N..TiCl.
'
4 4
4
4 4
4
49
49
47
6 57
55
S^N.^SO. , S N . 4 S 0
, S N TeBr
, S ^ N ^ S b F ^ ' , S„N„.4SbF
44
3
4 4
3
4 4
4 ' 4 4
5
' 4 4
5
52.53
, ,52,53
56
54
4 44
' S N .MoCl (?)
' , S N .VC1
, S^.BClg
,
due
o
S
N
W C L
4
S N .BBr
4
4
54
3
4
not
2
4
2
4
5
4
, S N .BCl .SbCl
S N .Se Cl (?)
4
c
5 3
4
3
6
' ,
54
5
, S N
4
S N .2TiCl (?)
4
4
4 <
5 3
3
unambiguously e s t a b l i s h e d .
4
4
57 6
57 6
2SbBr
' , S^.Mblg
'
3
6
' .
Adducts q u e r i e d a r e
F u r t h e r a d d u c t s w i t h many
metal h a l i d e s a r e discussed i n the experimental
X - r a y s t u d i e s on two o f t h e s e a d d u c t s
other
section.
(S N »SbClg,
4
4
58.59
S N . B F ) h a v e been p u b l i s h e d
4
4
3
.
of a n e i g h t membered s u l p h u r - n i t r o g e n
The s t r u c t u r e s c o n s i s t
r i n g , w i t h one o f t h e n i t r o g e n
atoms, bonded t o t h e antimony o r b o r o n atom.
s u l p h u r atoms form a s q u a r e
T h i s conformation d i f f e r s
atoms a r e s q u a r e
I n adducts t h e
and t h e n i t r o g e n atoms a t e t r a h e d r o n .
from t h a t o f S N
4
4
i n which t h e n i t r o g e n
p l a n a r and t h e s u l p h u r atoms (two above and two
-12-
b e l o w ) form a s l i g h t l y
and
elongated
tetrahedron.
Infrared
spectra
s t r u c t u r e o f many new S^N^ a d d u c t s w i t h L e w i s a c i d s a r e
considered i n the discussion.
Lewis-acid
b e h a v i o u r o f S^N^ i s u s u a l l y f o l l o w e d by
2
ring contraction
or degradation
that nucleophiles
.
The o b s e r v a t i o n s
invariably attack
suggest
t h e more e l e c t r o p o s i t i v e
atoms, v i z : s u l p h u r atoms a s would be e x p e c t e d .
A l l forms o f
6
n u c l e o p h i l i c a t t a c k on S^N^ b r e a k down t h e r i n g .
The o n l y
one w h i c h may have t h e r i n g p r e s e r v e d i s t h e t h i a z y l f l u o r i d e a d d u c t
2
(it
i s not w e l l c h a r a c t e r i z e d
) w h i c h c a n be made by r e a c t i o n
IF
19
5
f l u o r i n a t i n g a g e n t s , on S N
^4^4
* *2
of v a r i o u s
+
S N (NSP) ).
4
4
4
60
R u f f and G e i s e l
showed t h a t S N
4
and ammonia g i v e an
4
ammoniate o f t h e c o m p o s i t i o n S.N ,2NH .
S„N
g i v e s a n ammoniate S N . NH *.
X-ray patterns
I n a similar reaction
However a c c o r d i n g t o
and t h e a b s o r p t i o n s p e c t r a , t h e two compounds
a p p e a r t o be i d e n t i c a l and s i n c e S N
c a n be s u b l i m e d from
ammoniates e v e n a t room t e m p e r a t u r e , i t i s assumed t h a t
i s cleaved
appears t o r e s u l t
t r i p h e n y l p h o s p h i n e and S ^
61
(C„H_)_PN.S )
The f o l l o w i n g
6 5 3 4 o
for ( C H ) P N S .
0
5
4
4
d u r i n g t h e r e a c t i o n w i t h ammonia.
Ring contraction
6
S N
these
3
4
3
from t h e r e a c t i o n o f
+ 2P(C H )— r r * S P C C g H ^
g
5
s t r u c t u r e h a s been p r o p o s e d
+
-13-
•N
S _ N ^ = T
(C H )
=
6
5
3
62.129(a)
Reactions w i t h Grignard reagents
S
cause r i n g
degradation
N
4 4
(C_H_MgBr
» C^H SN=S=NSC^H, ) .
Complete d e g r a d a t i o n
6 5
bo
bo
63
h a s been o b s e r v e d i n t h e r e a c t i o n o f S„N. w i t h C-.H.PCl4 4
6 5
2
( c ) R e a c t i o n s o f S^N^ i n p o l a r s o l v e n t s
c
r
I n p o l a r s o l v e n t s more i n v o l v e d r e a c t i o n s o f S^N^ w i t h
L e w i s a c i d s have been found t o o c c u r
and
spectroscopic
established
obtained,
69
10
.
X-ray
70
, and c h r o m a t o g r a p h i c i n v e s t i g a t i o n s
have
that products
o f t h r e e main s t r u c t u r a l t y p e s may be
M
containing: ( i )
N
S
2
2
f
i
v
e
m
e
m
b
e
r
e
d
66 67
65
Ni(MeN S ) '
and Pt(HN S ) ) ; ( i i ) MNS
Co
(Pd(NS ) )
g
64
,
r i n g s (PbNgSgjNHg
f i v e membered r i n g s
HC\
*
2
.^
64-68
diffraction
; and ( i i i )
and Pd compounds*^'
7
0
) .
both
and MNS^ r i n g s (Co, N i
I n dimethylformamide, copper ( I I )
71
c h l o r i d e and bromide g i v e low y i e l d s o f SgNg.CuClg and S^Ng.CuBrg
70
73 74
I n m e t h y l o r e t h y l a l c o h o l , c o b a l t , n i c k e l and p a l l a d i u m
h a l i d e s r e a c t to give mixtures
three types.
'
'
w h i c h i n c l u d e compounds o f a l l
I n organic solvents S N
4
4
reacts with
selenium
d i c h l o r i d e t o g i v e t h i o t r i t h i a z y l c h l o r i d e , S^NgCl and e l e m e n t a l
selenium,
w h e r e a s i n t h i o n y l c h l o r i d e t h e same r e a c t i o n may
g i v e s e l e n o t r i t h i a z y 1 h e x a c h l o r o s e l e n a t e , Se_S N , S e C l _ , c o n t a i n i n g
£t b b
b
75
a three-element p i - d e l o c a l i z e d c a t i o n
.
R e a c t i o n s o f S^N^
-14-
w i t h s e v e r a l iiitjtal h a l i d e s i n t h i o n y l c h l o r i d e
and
have b e e n
studied
products of v a r i e t y of s u l p h u r - n i t r o g e n - m e t a l r a t i o s have
10,76
been obtained
'
e.g.
The
compounds c o n t a i n
and
(SN)
2
rings or chains
units; vibrational spectra
n
most l i k e l y
The
SNMnClg, S N C o C l g . , S N Z r C l
values
for
structures
2
4
, Sgl^CrClg.
i n v o l v i n g m e t a l atoms
s u g g e s t 2,3 and 4 a s t h e
n"^.
o f t h e s e compounds i n v o l v e
units of the
t y p e 1-3 10
C I M.S.N:S:N.MC1
(i)
(ii)
N:
s
MCI
Ii
CI
(iii)
MCI
x
( d ) Some o t h e r i m p o r t a n t r e a c t i o n s
An
i m p o r t a n t group
function
reactions
ring;
o f S^N^
of reactions
illustrating
the
o f t h e t e t r a n i t r i d e i s w i t h hydrogen h a l i d e s .
basic
These
may w e l l b e g i n w i t h p r o t o n a t i o n o f a n i t r o g e n atom i n t h e
i n the c a s e o f hydrogen c h l o r i d e ,
t h e f i r s t product o f r e a c t i o n
i n c a r b o n t e t r a c h l o r i d e i s a d a r k r e d p r e c i p i t a t e w h i c h i s thought
t o be S^N^.HCl.
E s p e c i a l l y i n the p r e s e n c e o f water, t h i s
changes
-15-
b
to t h i o t r i t h i a z y l c h l o r i d e .
The o v e r a l l r e a c t i o n i s c o n s i s t e n t
85
with a process proceeding
S
N
+
H
C
1
S
N
4 4
*
4'
S„N„.HC1 + 3HC1
4 4
H
4
by t h e f o l l o w i n g s t e p s
C
1
(
r
e
,
d
Precipitate)
> S „ N C 1 + NH„C1 + C l
4 3
4
2
0
0
W i t h HBr o r HI i n CC1., S N B r o r S.N„I i s b e l i e v e d t o be formed
4'
a t once .
4 3
4 3
With e x c e s s HI i n a n h y d r o u s f o r m i c a c i d , S^N^
i s completely
b r o k e n down ( S N
4
6
+ 1 2 H I — » 4 S + 61^ + 4NH ) .
4
g
T e t r a s u l p h u r t e t r a n i t r i d e r e a d i l y undergoes base h y d r o l y s i s
(2S N
4
4
+ 6 0H~ + 9 H 0 — » 2 S 0
2
This result
3
2
g
~
+ S ^
2
"
+ 8NH )
8 6
3
i s t y p i c a l f o r a substance with sulphur i n the plus
t h r e e o x i d a t i o n s t a t e , s i n c e i t c a n r e a d i l y undergo d i s p r o p o r t i o n a t i o n
to sulphur
( I I ) and su&phur ( I V ) .
t h a n h y d r a z i n e ) and p r o d u c t s
Formation
t h a n N-N bonds.
c o n t a i n s S-S bonds
T e t r a s u l p h u r t e t r a n i t r i d e a l s o undergoes
87
acid hydrolysis
When S N i s r e a c t e d w i t h S O C l ^ i n t h e p r e s e n c e
4
(rather
c o n t a i n i n g S-S bonds i s c o n s i s t e n t
w i t h t h e s t r u c t u r e o f S„N.; t h e m o l e c u l e
4 4'
rather
o f ammonia
4
a r s e n i c t r i c h l o r i d e or n i t r i c
S
o f SO^,
N
o x i d e , t h e compound 3 2 ° 2
i
s
80 81
obtained
'
.
I t i s a l s o obtained
by t h e r e a c t i o n between
82
ammonia and SOClg
.
Recently
i t h a s been shown t h a t SgNgOg
75 83
is
formed i n s m a l l y i e l d s
It
i s a l s o obtained
i n t h e r e a c t i o n between S N
4
by t h e r e a c t i o n between S N
4
4
4
and S O C l g .
and c e r t a i n
metal
'
-16-
h a l i d e s i n SOClg
The
83
.
c r y s t a l s t r u c t u r e o f S„N 0
O
£i
shows t h a t t h e
£i
of
m o l e c u l e c o n s i s t s o f a p l a n a r z i g - z a g c h a i n y ^ s u l p h u r and n i t r o g e n
atoms, a s shown below:
0
T h i o d i t h i a z y 1 d i o x i d e r e a c t s w i t h SbCl,. and T i C l ^ t o g i v e
S^N^.SbCl^ and S ^ N ^ , 2 T i C l . , r e s p e c t i v e l y
44
5
4 4
4
Tetrasulphur
84
t e t r a n i t r i d e reacts with
cyclopentadiene
i n a n i n e r t s o l v e n t a t 135-136°C and g i v e s S N . 4 C H .
4
a s i m i l a r way compounds S^^.2,Q^A
prepared
and S N
4
4 <
by t h e r e a c t i o n o f t h e n i t r i d e w i t h
4
5
g
In
2 C H g have been
7
bicycloheptene
79
( n o r b o r n e n e ) and b i c y c l o p e n t a d i e n e , r e s p e c t i v e l y .
Polymeric
sulphur n i t r i d e , (SN)
T h i s compound
dinitride
i s p r o d u c e d by t h e p o l y m e r i s a t i o n o f d i s u l p h u r
i n the absence of moisture.
The p o l y m e r i s a t i o n i s
b e s t e f f e c t e d by l e a v i n g d i s u l p h u r d i n i t r i d e
o
o 6
d e s i c c a t o r f o r 30 d a y s a t 20 - 25 C .
and
i n an evacuated
The p r o d u c t
i sstable
forms f i b r o u s c r y s t a l s up t o 3mm l o n g w i t h a s h i n y ,
brass-like
appearance.
6
-17-
The
p o l y m e r shows e v i d e n c e o f d e r e a l i z a t i o n .
It is
42
d i a m a g n e t i c and
conducts e l e c t r i c i t y
s t a b l e than S^N^.
at
1225
cm
The
^ w h i c h was
f o r a bond l e n g t h
of
.
The
p o l y m e r i s more
i n f r a r e d , s p e c t r u m showed a s t r o n g
attributed
5
1.48A .
t o an S=N
stretching
A band a t 1015
cm
band
vibration
1
was s u g g e s t i v e
42
of an S-N mode w i t h a more s i n g l e bond c h a r a c t e r
.
The o p t i c a l
s p e c t r u m showed a s t r o n g a b s o r p t i o n n e a r 7000A* w h i c h might i n d i c a t e
77
the p r e s e n c e o f a p i - e l e c t r o n d e l o c a l i s e d
conductance of
the
polymer i n c r e a s e d
also with r i s i n g pressure.
explained
chain
The
system
.
with r i s i n g
The
temperature
and
s e m i c o n d u c t a n c e b e h a v i o u r might
i n terms of p i - e l e c t r o n d e r e a l i z a t i o n
along the
i n a s i m i l a r manner to t h e d e r e a l i z a t i o n of
the
be
polymer
cyclic
42
tetramer
.
E a c h n i t r o g e n atom c a n
t o t h e p i s y s t e m and
pair electrons
or
each sulphur can
one
p h y s i c a l d a t a c o u l d be
or
two
contribute
contribute
3d-pi e l e c t r o n s .
one
two
p-pi
3p-pi
However
electron
lone-
the
r a t i o n a l i s e d i n terms of a s t r u c t u r e
c o n t a i n e d a l t e r n a t i n g s e q u e n c e of
greater
and
less pi
character
Tetrasulphur d i n i t r i d e
c
a
n
b
e
which
77
P r e p a r e d by t h e f o l l o w i n g methods:( a ) T e t r a s u l p h u r t e t r a n i t r i d e i s heated with carbon
o
.6
d i s u l p h i d e i n an a u t o c l a v e a t 120 C, ( p o o r y i e l d ) .
( b ) I t i s p r e p a r e d i n 42% y i e l d by t h e r e a c t i o n between
-18-
d i s u l p h u r d i c h l o r i d e and a s u l p h u r - n i t r o g e n - m e r c u r y compound
C S
(Hg (NS)
5
g
+ 4S C1
2
2
2
» 4S N
4
2
+ 3HgCl
6
Hg Cl ) .
+
2
2
2
( c ) H e a t i n g t o 80°C, t h e r e a c t i o n p r o d u c t s from s u l p h u r
g
d i o x i d e and ammonia .
T e t r a s u l p h u r d i n i t r i d e has an u n p l e a s a n t
odour and m e l t s a t 2 3 ° C . ^
No p h y s i c a l s t r u c t u r e d e t e r m i n a t i o n h a s been r e p o r t e d
6
and t h e f o l l o w i n g u n s y m m e t r i c a l c y c l i c
. / X
Polymeric sulphur
f o r m u l a h a s been proposed
.
N
nitrides
The n i t r i d e s S ^ N g and S^gNg a r e d e r i v e d from t h e e i g h t membered r i n g s y s t e m o f h e p t a s u l p h u r i m i d e .
condensing
this
They a r e made by
imide i n carbon d i s u l p h i d e s o l u t i o n s w i t h sulphur
6
d i c h l o r i d e or d i s u l p h u r d i c h l o r i d e r e s p e c t i v e l y
i n f r a r e d s p e c t r a a r e f e a t u r e l e s s e x c e p t broad
stretching region .
.
Their
bands i n t h e S-N
They have t h e f o l l o w i n g s t r u c t u r e s ,
-N—S
N
S
( x = l or 2)
-19-
Sulphur-nitrogen-halogen
compounds
T h e s e compounds have i n t e r e s t i n g c h e m i c a l
and
structural properties.
triple
They c a n c o n t a i n s i n g l e , d o u b l e and
bonds a s w e l l a s l o c a l i z e d
rings.
( s e e below)
and d e l o c a l i z e d p i - b o n d s i n
R i n g s w i t h d e l o c a l i z e d d o u b l e bonds may be c o n s i d e r e d
88
as i n o r g a n i c aromatic
compounds
( i ) Monomeric t h i a z y l h a l i d e s
The
t h i o n i t r o s y l h a l i d e s S=N-F, S=N-C1, and n i t r o s y l
0=N-F, 0=N-C1 a r e i s o m e r i c w i t h N^S-F and N=S-C1 and
respectively.
In reality
halides,
N=5-F, N=5-C1,
o n l y n i t r o s y l h a l i d e s ONF, 0NC1 and
t h i a z y l h a l i d e s NSF, NSC1 a r e known.
The monomeric
nitrosyl
bromide, BrNO i s known b u t monomeric NSBr h a s not y e t been
prepared.
In t h e n i t r o s y l h a l i d e s t h e halogen i s a t t a c h e d to n i t r o g e n , whereas
i n t h e t h i a z y l h a l i d e s i t i s a t t a c h e d t o nAtifegOR.
has
been a s c r i b e d t o t h e f a c t
itself
This
t h a t t h e h a l o g e n atom would
f o r p r e f e r e n c e t o t h e atom o f l o w e s t
join
electronegativity
i n t h e s e compounds^.
(a) Thiazyl chloride
NSC1 i s p r e p a r e d
by t h e d e p o l y m e r i s a t i o n o f t r i t h i a z y l
90 91
trichloride
'
S„N„C1„ s u b l i m e d
.
I n a c o n t i n u a l l y evacuated
sublimation
v e r y s l o w l y a t 55°C, t o a w a t e r
apparatus,
cooled c o l d - f i n g e r
g i v i n g y e l l o w S^N^Cl^ on t h e c o l d - f i n g e r w h i l e o n l y t r a c e s o f
NSC1 were pumped o u t .
However, when 40 mm p r e s s u r e o f n i t r o g e n
-20-
o r h e l i u m was p r e s e n t d u r i n g c l o s e d s u b l i m a t i o n a t 70-80^C, t o
a l i q u i d nitrogen cold-finger a yellow-white
white
to purple c r y s t a l s ,
f i l m , and
later
c o l l e c t e d , w h i c h v i r t u a l l y a l l pumped
out when warmed t o 20°C and p r o v e d t o be NSC1 w i t h l e s s t h a n
of the m a t e r i a l remaining
as S N C L .
o o
91
The e x p e r i m e n t s
o
5%
involving
d e p o l y m e r i s a t i o n of S^N^Cl^ i n d i c a t e d t h a t the d e p o l y m e r i s a t i o n
i s a r e v e r s i b l e p r o c e s s , and t h e f o l l o w i n g r e a c t i o n s e q u e n c e
i s p r o p o s e d on t h e b a s i s o f t h e known s p e c i e s i n v o l v e d
during
91
the
depolymerisation
S,N„Cl„(s) .
S„N Cl„(g)
S N Cl (g),
3NSCl(g)
2NSCl(g);==?
N (g) + S C l ( g )
3
n
o
OO
3
o J
3
2
2
3
3
( i i )
2
S Cl (g) + S N Cl (s)
2
( i )
o
3
( i i i )
2
»S N Cl (s) + NSCl(g)+SCl
3
2
2
2
2SCl (g);=e S Cl (g) + Cl (g)
2
2
Cl (g) + S N C1
2
3
2
2
The
2
3
3
(vi)
2
S Cl (g) + S N Cl (s)
2
(v)
2
» 2NSCl(g) + S C l ( g )
2
3
(iv)
»S N Cl (s)+NSCl(g)+SCl (g) ( v i i )
p r o c e s s e x p l a i n s t h e observed
3
2
2
2
a u t o c a t a l y t i c behaviour
enhanced o c c u r r k n c e o f s t e p 3 w i t h b u i l d up o f N S C l ( g ) .
by t h e
-21-
89,92
The
I'
f o l l o w i n g methods a l s o have been u s e d t o p r e p a r e NSC1
( i ) When a s t r e a m
i n t o a stream
o f aobiuu^ d i s u l p h u r d i c h l o r i d e was p a s s e d
o f a c t i v e n i t r o g e n , NSC1 i s formed (2N +
S^Cl^—»
2NSC1).
(ii)
I t i s prepared
by h e a t i n g under r e f l u x a
suspension
of ammonium c h l o r i d e i n e x c e s s o f d i s u l p h u r d i c h l o r i d e (NH C1 +
4
2S C I
¥ 3S + NSC1 + 4HC1).
(iii)
I t i s an i n t e r m e d i a t e
i n the p r e p a r a t i o n o f S^N^Cl^
from SgNgClg and c h l o r i n e , a n d c a n be i s o l a t e d
(SgNgClg + C l
»
2
2NSC1 + S C 1 ) .
2
and
( i v ) When S N C I
i s heated
S C 1 a r e e v o l v e d ( 3 S NgClg
2
( v ) NSC1 c a n be o b t a i n e d
i n vacuo t o 8 0 - 9 0 ° C , NSC1
> 3 2
2 '
S
N
C 1
+
2
N
S
C
1
+
S
C
1
)
by t h e a c t i o n o f c h l o r i n e on
g a s e o u s NSF.
Thiazyl chloride i sa greenish-yellow
gas.
I t r e a c t s with
w a t e r t o g i v e ammonia, s u l p h u r d i o x i d e and h y d r o c h l o r i c a c i d
(NSC1
+ H 0
2
It
attached
»HNSO + HC1; NHSO + H 0
2
» NH
g
+ SOg).
i s p o s s i b l e t h a t NSC1 h a s t h e s t r u c t u r e w i t h c h l o r i n e
to n i t r o g e n , but the very high value of force
constant
o
95 96
( 1 0 . 0 2 m d y n e s / A ) and t h e NS bond o r d e r ,
*
2.3 show t h a t o n l y
the s t r u c t u r e i n which c h l o r i n e i s a t t a c h e d
s i n c e i n t h e c a s e o f SNC1 no e x p a n s i o n
to sulphur
i s likely,
of the valency s h e l l
of t h e
-22-
nitrogen i spossible
93
2.
t o g i v e a bond o r d e r N
According
No
94
t o t h e Walsh r u l e
, NSC1 s h o u l d
assymetric molecule gives
rise
be n o n - l i n e a r .
(according
A
non-linear
t o t h e r e l e v a n t symmetry
c o n s i d e r a t i o n s and s e l e c t i o n r u l e s ) t o t h r e e v i b r a t i o n a l
of freedom, c o n s t i t u t i n g t h r e e fundamental frequencies,
v^NS s t r e t c h i n g ) ,
v ( S C l s t r e t c h i n g ) and
2
bending v i b r a t i o n ) .
1
t o 4000cm
1
and
),
V (273
93
and
combination
namely
v ( t h e NSC1
g
The i n f r a r e d s p e c t r u m o f NSC1 ( f r o m 300
) showed t w o f u n d a m e n t a l f r e q u e n c i e s ,
v„(414 cm
degrees
bands
.
cm
v ^ ( i 3 2 5 cm
was c a l c u l a t e d f r o m
I t was c o n f i r m e d
1
),
t h e overtone
t h a t NSC1 h a s t h e
s t r u c t u r e NSC1 w i t h C symmetry a n d i s n o t SNC1.
(b) Thiazyl f l u o r i d e
o
g
NSF i s a n u n s t a b l e
It
c o l o u r l e s s g a s (m.p. -89 C ,
o
b . p . 0.4 C ) .
c a n be p r e p a r e d b y s e v e r a l m e t h o d s g i v e n b e l o w , ( m i n o r
shown i n b r a c k e t s ) .
CC1
(i)
NH
+ S + 4AgF
(ii)
NH
+ SF
(iii)
F S=N-C0F
> NSF + 3HF + 4AgF (NSF )
» NSF + 3HF
VNSF + C 0 F
2
2
400°C
(iv)
NF
+ S
3
» NSF ( S F ,
2
F
(v)
S N
4
4
2
SF )
4
(-75°C)
* NSF ( N S F , S F )
3
4
products
-23SeF4(-10°C)
:
» NSF ( S O F , S i F , S e )
(vi)
S N
(vii)
S^N .4SbF
4
4
2
4
145°C
/1
4 4
> NSF
c
0
AgF ,HgF
2
(viii)
S N
4
2
» NSF
4
CC1„
4
SF
(ix)
S N
4
The
> NSF
4
f l u o r i n a t i o n o f S.N, u s i n g AgF„ o r HgF.., i n b o i l i n g
4 4
2
2
CC1_ i s a s u i t a b l e m e t h o d .
4
I n t h e c a s e o f HgF_. t h e f l u o r i n a t i o n
2
proceeds under m i l d e r c o n d i t i o n s and b e t t e r y i e l d s a r e o b t a i n e d .
NSF i s a b e n t t r i a t o m i c m o l e c u l e w i t h s u l p h u r
middle
a
and f l u o r i n e atom a t t a c h e d
thiazyl
t o sulphur
97 98
i n the
.
After
NSFg,
f l u o r i d e h a s t h e h i g h e s t SN b o n d o r d e r o f a l l t h e s u l p h u r 32
nitrogen halides
correspond
The
SF
4
.
The b o n d o r d e r o f more t h a n t w o w o u l d
t o r e s o n a n c e s t r u c t u r e s shown b e l o w ,
NSF m o l e c u l e c a n b e t h o u g h t
o f as b e i n g d e r i v e d
w i t h t h r e e o f t h e f l u o r i n e atoms r e p l a c e d by a t r i p l y
n i t r o g e n atom.
from
bonded
T h e SF d i s t a n c e i n NSF i s t h e same a s t h e
SF d i s t a n c e i n S F
4
a n d t h e SN d i s t a n c e o f NSF i s o n l y
98
g r e a t e r t h a n t h e SN d i s t a n c e i n NSF^.
slightly
-24-
NSF i s h i g h l y
r e a c t i v e and undergoes h y d r o l y s i s w i t h
97,98
water
vapour y i e l d i n g
thionyl
i m i d e , HNSO, a s a n i n t e r m e d i a t e
The
f i n a l h y d r o l y s i s p r o d u c t s a r e s u l p h i t e , f l u o r i d e a n d ammonia,
the
course
o f t h i s r e a c t i o n has n o t y e t been e l u c i d a t e d .
c o p p e r o r t e f l o n v e s s e l s , NSF c a n b e s t o r e d f o r a s h o r t
without decomposition,
but i t trimerises t o S N F
O
It
decomposes s l o w l y i n g l a s s v e s s e l s .
glass proceeds r a p i d l y
O
In
time
on s t a n d i n g .
«J
The r e a c t i o n w i t h
a t a b o u t 200°C a n d g i v e s
S
4
N ,
S
0
4
F
2
s
»
°2
32
S i F . and N
.
NSF p o l y m e r i s e s t o g i v e S N~F„ a t h i g h p r e s s u r e s ,
at
w h e r e a s /low p r e s s u r e s , g r e e n - y e l l o w c r y s t a l s o f S^N^Fg s e p a r a t e
4
2
3
out on t h e w a l l s o f t h ec o n t a i n e r .
J
3
NSF f o r m s a c o l o u r l e s s
90,100
c r y s t a l l i n e adduct w i t h boron t r i f l u o r i d e
+
NSF.BF„ o r NS BF
and
.
T h x s compound
i s s t a b l e f o r a short time a t low temperatures
6
d i s s o c i a t e s i n t o x t s components xn t h e gas phase .
( i i ) Polymeric
(a)
thiazyl halides
Polythiazyl
bromide
When b r o m i n e i s a l l o w e d t o r e a c t w i t h S^N
d e e p - r e d b r o w n compound o f c o m p o s i t i o n
The
infrared
section.
It
spectrum
i n CSg,
1
x
is obtained^'^ .
o f t h i s compound i s g i v e n i n t h e e x p e r i m e n t a l
I t i s s t a b l e i n dry
i s thought
(NSBr)
4
a i r , buthydrolysed
i n moist a i r .
t o be a b r o m i n e d e r i v a t i v e o f ( S N ) ^ a n d t h e
f o l l o w i n g s t r u c t u r e has been proposed.^
-25-
-(S
= N)
X
Br
It
reacts
w i t h ammonia a t
-40°C t o g i v e
a redsolution
(probably
Q
(NS-NH ) ) a n d ammonium b r o m i d e .
0
(b) T r i t h i a z y l
<
i )
S
N
3 3
C 1
t r i c h l o r i d e and t r i t h i a z y l
3
Trithiazyl
method o r i g i n a l l y
trifluoride
t r i c h l o r i d e may be p r e p a r e d by t h e
d e s c r i b e d b y Demarcay
127
a n d Meuwsen
102
and
117
most r e c e n t l y , r e v i s e d
chlorine
(3S.N
by Schroeder and Glemser
on p a s s i n g
t h r o u g h a s u s p e n s i o n o f S^N^ i n a n i n e r t
+ 6C1
A more c o n v e n i e n t m e t h o d r e c e n t l y
104
d e s c r i b e d by J o l l y and Maguire
u t i l i s i n g the reaction:
3S N C1 + 3C1
> 2S N C1
+
3SC1 .
3
2
»4S_N C I
solvent
2
).
2
T h i s method, b u t w i t h C C 1
3
4
3
3
solvent,
2
was f i r s t
d e s c r i b e d by
118
Meuwsen
.
sulphuryl
chloride
this
The p r e p a r a t i o n
o f SgNgClg f r o m S^N
4
using
as t h e c h l o r i n a t i n g a g e n t i s d e s c r i b e d i n
thesis.
I n t h e s t r u c t u r e o f S g N ^ l g shown b e l o w
Molecule of (NSCI)j. The atoms S(2), N(2) and Cl(2)
are on the mirror plane.
-26-
the molecule consists
s u l p h u r and n i t r o g e n
nitrogen
o f a s i x - m e m b e r e d r i n g compound o f a l t e r n a t i n g
atoms i n a c h a i r
atoms b e l o w t h e
configuration with
s u l p h u r a t o m s a n d one c h l o r i n e b o n d e d t o e a c h
s u l p h u r i n an a x i a l p o s i t i o n above t h e r i n g . ^ ' ' ' ^ ^
(marked C l ( 2 )
on the p r e v i o u s diagram) d i f f e r s
compare (NSOCl)^• ^ 0 , 1 9 0
atoms c o n t r i b u t e
^
this
one e l e c t r o n
been proposed t o c o n s i s t
the three
One c h l o r i n e
from the o t h e r
atom
two -
s t r u c t u r e b o t h sulphur and n i t r o g e n
e a c h t o t h e it s y s t e m .
of nitrogen
p -sulphur d
Jt
These bonds have
overlap
delocalized
IT
3
e i t h e r over the
centre
entire ring
S-N-S b o n d s .
which i n d i c a t e s
4
3
3
0
a n d S.N.F..
3
4
4
T h e SN b o n d s a r e a l l s h o r t
4
threeo
(1'605A),
and equal
t h e p r e s e n c e o f it b o n d s . ^ 7 , 1 0 8
S-jN^Clg i s i n c o n t r a s t
S_N_F
as i n benzene o r o v e r s e p a r a t e
aromatic r i n g o f
t o t h e a l t e r n a t i n g s i n g l e a n d d o u b l e bonds o f
The p r e s e n c e o f l o c a l i s e d d o u b l e b o n d s i n S_N F„
0
3 3 3
19
is
deduced from
F n.m.r. d a t a ( t h e t r i m e r a n d t e t r a m e r f l u o r i d e show
88
similar
shifts);
d i s t a n c e s i n S^N^F^ a r e k n o w n
115
88
f r o m an X-ray s t r u c t u r e d e t e r m i n a t i o n .
Glemser
explains the
different
the
sulphur-nitrogen
r i n g bonding i n the
c h l o r i d e and f l u o r i d e s as f o l l o w s ( c f .
2
Allen
) : "Each f l u o r i n e a t o m p o l a r i z e s
electrons,
t o such an e x t e n t
the sulphur,
by drawing o f f
t h a t , i n c o m p a r i s o n t o S^N^, a w e a k e r
repulsion
between t h e l o n e e l e c t r o n p a i r on the S and t h a t on the N
results.
I n t h i s way, t h e b o n d l e n g t h
towards formation
and
c a n be d e c r e a s e d and t h e t e n d e n c y
o f a d o u b l e bond i s enhanced.
Alternating
l o n g e r S-N d i s t a n c e s may f r e q u e n t l y be more f a v o u r a b l e
proportionately
shorter,
b u t equal distances,
shorter
than two
s u c h as o c c u r i n
-27-
delocalized
bonds.
energy i n c r e a s e s
the
T h a t i s t o s a y , t h e a t t r a c t i o n term o f t h e bond
exponentially
w i t h decreasing
d i s t a n c e , so t h a t , i n
case o f a l t e r n a t i n g d i s t a n c e s , t h e g a i n i n double
exceed t h e d e l o c a l i s a t i o n energy f o r equal
distances.
intensified
by t h e p o s i t i o n o f t h e f l u o r i n e , w h i c h
N=S-F a n g l e
a s w i d e a s p o s s i b l e , as i s e v i d e n c e d
b o n d e n e r g y may
This e f f e c t i s
tends
t o f o r m an
by t h e s t r u c t u r e o f
N. S.F
N
N
106*2
F
The
same a s s u m p t i o n s m u s t be v a l i d f o r N^S^F-j*
the c h l o r i n e
cannot p o l a r i z e
i n N^S^F^.
I n N^S^Cl^ , h o w e v e r ,
t h e s u l p h u r as s t r o n g l y
as f l u r d n e c a n
T h e r e f o r e , no p r e p o n d e r a n c e i s g i v e n l o c a l i z e d
double
b o n d s a n d S-N d i s t a n c e s a r e l o n g e r , i . e . t h e s y m m e t r i c a l
arrangement
of chlorine
favoured."
a n d t h e g a i n i n d e l o c a l i z i n g e n e r g y a r e more
Trithiazyl
trichloride reacts with
sulphur
t r i o x i d e and g i v e s
a p a l e - y e l l o w a d d u c t S^N^Cl^^SO^ a n d t h e n t h e o l i v e - c o l o u r e d
S N C1 .6S0 .
3
3
3
3
6
When t h e s e a d d u c t s
a-sulphanuric chloride
S N C1 0
3
3
3
3
a r e heated
i s formed.
t o 140-160°C, P
The s t r u c t u r e o f oc-
1 U
U1
-A u
u
At. j
108,109,110
s u l p h a n u r i c c h l o r i d e has been d e t e r m i n e d .
'
'
show t h a t a - s u l p h a n u r i c
(like
chloride
.
The r e s u l t s
i s t r i m e r i c w i t h a n S.jN
S„N„C1, b u t w i t h o x y g e n a t o m s t a k i n g
l4
3
ring
the place o f lone
pairs
-27a-
on s u l p h u r ) .
The m o l e c u l e e x i s t s as t h e c h a i r f o r m w i t h t h e
c h l o r i n e atoms i n a x i a l
p o s i t i o n s a n d w i t h a l l S-N d i s t a n c e s
e q u a l ( 1 » 5 7 1 A ) ^ ^ as i n S^N^Cl^ t h e r e a r e t w o t y p e s o f a x i a l
,.
.
_
110,190
c h l o r i n e atoms.
'
m
„
,
The s h o r t n e s s a n d e q u a l i t y o f t h e
L
L
s k e l e t a l bonds p r o b a b l y d e n o t e s a p p r e c i a b l e P ~^ o v e r l a p ;
fl
also
seems l i k e l y
pair
t o sulphur,
that there
i t
n
i s d o n a t i o n o f the n i t r o g e n
lone-
42
t o form a co-ordinate
jt-bond
especially
s i n c e t h e s u l p h u r atoms i n ( N S O C l ) ^ have c o n s i d e r a b l e L e w i s
acidity
[sulphanuric
c h l o r i d e f o r m s an a d d u c t ( p y . N S O C l ) ^ w i t h
128
pyridine].
Two new s u l p h u r a n d n i t r o g e n c o n t a i n i n g
membered r i n g
compounds (S^N^Cl^O a n d S.jN.jF2ClO) have
sixrecently
111
been r e p o r t e d .
liquid
C h l o r i n a t i o n o f S^NgOg, b y means o f
chlorine yields
sulphanuric
ring
the c r y s t a l l i n e c o l o u r l e s s
compound, S^N^Cl^O; w i t h s i l v e r
S^N^Cl^O g i v e s a n o t h e r c o l o u r l e s s
^3^3^2^^"^'
^
e
difluoride
ring
compound
n
Conformations s i m i l a r
t o ( N S C l ) ^ ( p . 25)
( N S O C l ) ^ ( b e l o w ) a r e t o be e x p e c t e d , i . e . a x i a l
atoms.
thiazyl-
^°^--'- ^ 8 s t r u c t u r e s have been p r o p o s e d f o r
t h e s e compounds.''"^''"
and
ow
crystalline
mixed
halogen
1
Molecule of o(NSOCI)j. Tin u r n SU). N(J). 0(2).
and Cl(2) ire on the mirror plane.
-28-
^Cl
0.
CI
N
N
N
N
I
I I
I
I I
s
/ \
/
\
1/
:i
/ \
Cl
F
/
N
The t h e r m a l d e p o l y m e r i s a t i o n o f S N C l
o o
chloride
\F
has a l r e a d y been d e s c r i b e d
(page
t o form
thiazyl
o
20).
S N Cl
i s
/
easily
h y d r o l y s e d by w a t e r ,
acqueous a c i d
or alkali,
presumably
Q
by n u c l e o p h i l i c
attack
on s u l p h u r
Ammonolysis o f t r i t h i a z y l
, g i v i n g ammonia a n d c h l o r i d e .
t r i c h l o r i d e p r o d u c e s t h e amide
12
(H.N-SN)_
.
I f t h ef r e s h l y prepared
amide i s d i s s o l v e d i n
a c q u e o u s ammonia a n d t h e n r a p i d l y p r e c i p i a t e d
with
silver
n i t r a t e a v e r y e x p l o s i v e y e l l o w s i l v e r s a l t c a n be i s o l a t e d
112
r e m o v i n g ammonia u n d e r vacuum
.
The f o l l o w i n g p r o b a b l e
12
s t r u c t u r e h a s b e e n p r o p o s e d f o r t h e s i l v e r compound
.
S
\
N
N
I
I
HN=S
S=NH
I
Ag
after
-29-
S N CI
r e a c t s w i t h d i m e t h y l s u l p h o x i d e g i v i n g new t y p e o f
sulphur-nitrogen cation
_
(SgNgClg + 6 ( C H ) S O — * 3
3
CI
+ 3S0 ) .
When t r i t h i a z y l
trichloride
3
2
i sallowed
w i t h tetrasulphur tetraimide or heptasulphur
of
[(CH ) S=N=S(CH ) ]
2
3
Q
pyridine,
t o react
imide i n t h e presence
t e t r a s u l p h u r t e t r a n i t r i d e i s formed, suggesting
+
88
a n d N=S i o n s i n t h e s e r e a c t i o n s
—
the
f o r m a t i o n o f b o t h t h e N33
(4S N Cl
g
6 S
3
N
+
4 4
1
+ 3S N H
3
2
4
H
C
1
+
4
* 6S N
4
4
72S).
3
3
3
+ 12S NH—*
?
I f thereaction i scarried out i n the
absence o f p y r i d i n e , which
red
+ 12HC1; 4 S N C 1
4
i s i n t e n d e d t o c a p t u r e HC1, a b r o w n
adduct i s formed, which
r e a c t s w i t h traces o f water
t o give
88
S N C1
4
(S N .4HC1
3
4
Molybdenum
in
*S N C1 + Nl^Cl + Clg)
4
4
3
hexacarbonyl
.
reacts with t r i t h i a z y l
trichloride
d i c h l o r o m e t h a n e t o g i v e m i c r o c r y s t a l l i n e brown s o l i d ,
MoS N C I
113
(S_N C1
0
0
+ Mo(CO)„
* MoS„N_Cl
i n v o l v i n g metal-metal
bonding
being
insoluble i nnon-polar
of
3
S N C1
3
<">
to
3
S
N
+ 6C0)
0
A polymeric
structure
was t h o u g h t , o n t h e b a s i s o f i t s
s o l v e n t s and t h e observed
low r a t i o
Mo.
F
3 3 3
When NSF i s a l l o w e d t o s t a n d
for
t h r e e days, a m i x t u r e o f c r y s t a l s
can
be s u b l i m e d
i na sealed glass
container
i s formed from which
97
.
S
N
3 3^3
i
s
m
o
r
e
c o n v e n i e n t l y p r e p a r e d by
SgNgFg
2
-30-
Q7
f l u o r i n a t i n g S N CI
S N F
o
O
i n CCl
u s i n g AgF "".
i s a colourless, volatile,
crystalline
compound
O
(m.p. 74.2°C., b . p . 92.5°C) a n d s o l u b l e i n i n e r t
s o l v e n t s such
97
as b e n z e n e , C C l ^
.
No X - r a y s t r u c t u r e d e . t e r m a t i o n h a s b e e n
reported, b u t the c y c l i c
that
f o r m u l a c a n be i n f e r r e d
t h e r e i s o n l y one n u c l e a r magnetic
from the
resonance l i n e f o r f l u o r i n e ,
s h o w i n g t h a t a l l t h r e e f l u o r i n e atoms a r e i n e q u i v a l e n t
The
i n f r a r e d spectrum
_ 97
720 a n d 6 5 0 cm
.
o f S„N F
d
J
fact
environments
shows a b s o r p t i o n - p e a k s a t 1 0 8 5 ,
J
1
and
S^N^F^.
I t i s more m o i s t u r e s e n s i t i v e t h a n S N C I .
I t i s s t a b l e i n dry a i r and t u r n s b l a c k i n moist
6
a i r w i t h decomposition
.
I ncold diluted
sodium
hydroxide
32
s o l u t i o n SgN^Fg i s h y d r o l y s e d by t h e f o l l o w i n g r e a c t i o n
S
N
F
3 3 3
+
9 H
3
N
H
F
+
2° — >
4
(c) Tetrathiazyl
N
F
:i
s
^4 4 4 " P
on S N ^ i n C C l ^
4
3 H
r e
,
S 0
2 4'
tetrafluoride
P
a r e d
f r o m t h e r e a c t i o n o f AgFg
( t h e r e a c t i o n o f elementary
fluorine with
solid
88
S^N^ i s t o o v i o l e n t a n d g i v e s s u l p h u r f l u o r i d e s a n d n i t r o g e n )
b u t a t t e m p t s t o o b t a i n t h i s compound by t h e p o l y m e r i s a t i o n o f NSF
32
have been u n s u c c e s s f u l
.
I t i stherefore considered
that the
f o r m a t i o n o f S ^ ^ F ^ f r o m S^N^ a n d AgFg d o e s n o t i n v o l v e i n t e r m e d i a t e
SN r a d i c a l s b u t t h a t
t h e f l u o r i n e atoms add d i r e c t l y
s u l p h u r atoms o f t h e S^N^ r i n g .
t o the
-SI-
S'^N^F^ m o l e c u l e , has
a puckered eight-membered r i n g
of molecular s t r u c t u r e , w i t h the plane of the n i t r o g e n
type
atoms
2
above t h e p l a n e o f t h e
sulphur
atoms
measurements i n d i c a t e t h a t i n t h e
there
.
i n p a r t due
single
-Jt e l e c t r o n s , t h e r e f o r e
t o the
f a c t t h a t the
to a r e p u l s i o n of the
nitrogen
diffraction
t e t r a m e r i c f l u o r i d e . S„N.,F..
'
4 4 4
i s an a l t e r n a t i o n o f d o u b l e and
D e r e a l i z a t i o n of
X-ray
#
1
b o n d s
1
4
' .
i s minimal.
bonding i t s e l f
l o n e - p a i r , by
the
This i s
i s weak,
due
sulphur-lone-
5
pair
and
a l s o because t h e non-bonded i n t e r a c t i o n s ( l o n e - p a i r ,
polar
and
steric repulsions)
configuration.
p
d
p
irt
~
irt
n
- pft
b o n a
force the r i n g
t o assume a
T h i s reduces the p o s s i b i l i t y
n
^ S
c
a
n
occur.
An
that
tub
delocalized
a d d i t i o n a l f a c t o r which
limits
b o n d i n g t o a l t e r n a t e s k e l e t a l bonds i s t h a t
although
t h e r e i s a l a r g e o v e r l a p b e t w e e n a s u l p h u r d.
o r b i t a l and
n i t r o g e n p.jt o r b i t a l , t h e d 2 2 o r b i t a l , w h i c h i s d i r e c t e d
x—y
one
rt
t o w a r d s t h e p^
orbital
of the
other
neighbouring
nitrogen
5
i s not
polarized
Thus t h e
sufficiently
aromatic character
to form a strong
of the r i n g
n
bond
i s l o s t and
.
the
puckered
6
e i g h t - m e m b e r e d r i n g has
a different
s h a p e f r o m t h a t o f S^N^ .
97
I n f r a r e d bands
S
N
F
4 4 4
1
1
6
a
t
1
1
t h a t can
1
7
'
7 8 6
'
7 6 0
be
'
7 0 9
used f o r t h e
'
6
4
5
a
s t r u c t u r e o f S.N„F. i s shown b e l o w :
4 4 4
n
d
5
2
0
c
identification
m
_
1
«
T
n
e
of
-32-
FS ••••
N
SF
N
N
FS
S^N F
4
It
4
N
. i s a white
SF
c r y s t a l l i n e compound (m.p. 153°C
i s s o l u b l e i n CC1
(3.44g. p e r l i t r e
4
g r e e n a d d u c t F S N — » BF^ t h e t h e r m a l
4
4
o
6
a t 2 C) .
(decomp.)).
I tforms a
decomposition o f which
4
32
y i e l d s NSF
.
The compound h y d r o l y s e s
sodium hydroxide
(iii)
(S N F
4
4
4
i n warm
+ 12H 0-+NH F + 4H SN ).
Sulphur-nitrogen
Thiazyl
completely
2
4
2
halides derived
from
3
sulphur
trifluoride
NSF„ i s a d e r i v a t i v e o f SF„ i n w h i c h t h r e e
3
6
atoms a r e r e p l a c e d
to
hexafluoride
fluorine
by n i t r o g e n a t o m s a n d i t r e s e m b l e s t h e h e x a f l u o r i d e
some d e g r e e i n i t s s t a b i l i t y
6
a n d l a c k o f r e a c t i v i t y ..
I t
is
f o r m e d when ammonia i s p a s s e d i n t o a s u s p e n s i o n o f s u l p h u r
CC1
32
4
and A g F i n C C 1
(NH + S + 6AgF
* NSFg+3HF+6AgF).
2
4
g
2
NSF
i s a l s o f o r m e d i n a l l f l u o r i n a t i o n s o f S N w i t h AgF
CC1
4 4
.4
32
4
i n CC1
( S ^ N , + 12AgF„
^
4NSF + 1 2 A g F ) .
3
ft
NSF
b.p.
ft ft
O
A
i s a colourless, pugently
-27.1°C)^.
I t s molecular
s m e l l i n g gas (m.p.-72,6°C,
s t r u c t u r e has been e s t a b l i s h e d
s t u d i e s o f the m i c r o w a v e s p e c t r u m , i n f r a r e d s p e c t r u m a n d f l u o r i n e
6
nuclear magnetic resonance .
NSF i s i s o e l e c t r o n i c w i t h OPF„
O
O
from
-33-
( t e t r a h e d r a l , having the
symmetry C g ) w h i c h g i v e s
of
similar
i n f r a r e d spectrum to t h a t
bond
811,
32
.
775,
I n f r a r e d spectrum
52J., 429
and
342
1
cm
97
o f NSF
.
very
6,32
FClOg
.
The
f o r c e c o n s t a n t s c o r r e s p o n d s t o a bond o r d e r o f 2.7
SN
a
v
calculated
for
the
shows p e a k s a t
o
1515,
I t s s t r u c t u r e i s shown b e l o w :
N=S
The
chemical properties
also
seem t o i n d i c a t e t h a t i t i s
r e a s o n a b l e t o c o m p a r e NSF^ w i t h SFg.
3p and
sp
3d e l e c t r o n s
i n SF
3 2
d
s t a t e , the o r b i t a l s
are
two
p
NSF
.
The
- d^
r t
are
However, whereas t h e
hybridised
b
i n NSF
o
are
sp
3
to the
f a c t t h a t t h e F-N-F
octahedral
hybridised
o v e r l a p s b e t w e e n n i t r o g e n and
a n g l e i n NSF
3s,
32
.
There
the sulphur
(94°A) i s
in
smaller
than the
i d e a l t e t r a h e d r a l a n g l e i n d i c a t e s . some c o n t r i b u t i o n
o f d and
p states
32
Thiazyl
in
sulphur
f l u o r i d e does n o t
r e a c t a t room t e m p e r a t u r e
with
6
ammonia gas
but
.
I t reacts
i t i s h y d r o l y s e d by
slowly
w i t h w a t e r a t room
sulphuric
a c i d and
temperature,
f l u o r i d e i o n when
Q
b o i l e d w i t h sodium h y d r o x i d e s o l u t i o n .
m e t a l l i c s o d i u m and
reacts
only
I t is stable
towards
a t a b o u t 400°C t o f o r m Na^S,
-34-
nitrogen
and s o d i u m f l u o r i d e
NSF
reacts
w i t h BF
o
can
97
t o form colourless
NSF
o
b e p u r i f i e d by s u b l i m a t i o n .
88
.BF ,
which
o
o
I n f r a r e d measurements and
m o l e c u l a r w e i g h t d e t e r m i n a t i o n s i n d i c a t e t h a t t h e gaseous phase
consists
o f a n e q u i m o l a r m i x t u r e o f NSF
of t h e s o l i d b u t n o t t h e l i q u i d
resembles t h o s e o f t h e a l k a l i
compound
compound
.
The
i n t h e near
spectrum
infrared
metal tetrafluoroborates.
The
t o have t h e f o r m u l a 1 i n t h e
32
s t a t e and f o r m u l a 2 i n t h e s o l i d s t a t e
as shown b e l o w
liquid
i s therefore
a n d BF
assumed
FgS=N — > B F
+
[NSF ]
3
4
(1)
(2)
The i n s t a b i l i t y
o f these adducts i n d i c a t e t h a t the
donor power o f n i t r o g e n
In a d d i t i o n
[BF ~]
2
i s c o n s i d e r a b l y w e a k e n e d by t h e N=S
t o NSF , compounds
o
of the type,
CF„N=SF a n d SF_N=SF„ h a v e b e e n p r e p a r e d
3
4
5
2
bond.
F„NSF , F SNH ,
^
o
o
^
0
32
J1
( i v ) T h i o d i t h i a z y 1 m o n o c h l o r i d e j d i c h l o r i d e and
( i ) T h i o d i t h i a z y l c h l o r i d e , S^N^Cl,
was
difluoride
first
128
p r e p a r e d by Demarcay
S C1
0
.
, f r o m t h e r e a c t i o n b e t w e e n S^N^ a n d
I t c a n be o b t a i n e d by t h e vacuum s u b l i m a t i o n
n
RO—QO^P
a t 80-90 C ( 3 S N C 1
3
It
i s also
2
2
—
12*3
>
formed i n t h e r e a c t i o n
2
S
N
3 2
C
1
+
reacts
2
N
S
C
1
+
s
e
i
5
2
o f N0C1 w i t h S^N^ o r when
32
S N Cl
of SJ
w i t h NO i n n i t r o m e t h a n e .
CL
-35-
( i i ) Thiodithiazyl
d i c h l o r i d e , S N CI
was
103
reported
It
by Meuwsen
i n t h e c h l o r i n a t i o n o f S N CI
i n CC1 .
c a n be p r e p a r e d b y r e f l u x i n g a m i x t u r e o f S ^ C l ^ a n d ammoriium
chloride
(2NSC1 + S C 1
2
*
2
S
N
3
C
1
2
+
2
S
C
1
2
123
'
}
S
N
3 2
C 1
2
124
was f i r s t
SCI
by
i d e n t i f i e d by Demarcay
or S CI
t o react
the reaction
, who p r e p a r e d i t by
with S N .
of tetrachloro
allowing
I t may a l s o b e p r e p a r e d
ethylene
(or t r i c h l o r o ethylene)
125
with S N C1
3
3
3
.
An X-ray c r y s t a l s t r u c t u r e
that
and
analysis
t h e compound i s a s a l t c o n s i s t i n g
S N Cl
+
cation,
on S N C I
shows
of a chloride
t h e s u l p h u r and n i t r o g e n
anion,
atoms f o r m a
p u c k e r e d f i v e membered r i n g as shown b e l o w
CI
CI®
129(a)
S
The c h e m i s t r y o f 3
by
N
C
1
2
2
n
a
s
D
e
e
n
reviewed
S
( i i i ) Thiodithiazyl
difluoride, 3
t h e d e c o m p o s i t i o n o f NSF
in a sixlitre
N
F
2
2
i
s
P
r e
P
a r e d
glass f l a s k a t
88
p r e s s u r e s o f a b o u t 600 mm Hg
crystals
are obtained.
.
After
one week
greenish-yellow
SgNgFg s u b l i m e s a t 40°C a n d 55°C
y e l l o w i s h - g r e e n and b r i g h t - g r e e n
crystals
respectively
88
giving
-36-
B o t h t h e compounds a r e s o l u b l e
i n C C l ^ a n d h a v e t h e same
m o l e c u l a r w e i g h t s and u l t r a v i o l e t
are
( t h e t w o compounds
t h o u g h t t o be p o l y m o r p h i c m o d i f i c a t i o n s o f t h e same c o m p o u n d ) ,
S i n c e S^N^Fg i s s o l u b l e
to S N CI
i n CCl^, an i o n i c s t r u c t u r e s i m i l a r
i s less p r o b a b l e , and a s t r u c t u r e , which i s g i v e n
below i s proposed on t h e basis
of
spectra
i t s nitrogen
of thequalitative
conversion
t o ammonia by a l k a l i n e h y d r o l y s i s
F-S-N=S=N-S-F
(v) Thiotrithiazyl
halides
T h i o t r i t h i a z y l halides
seven-membered r i n g S^Ng*.
contain
thecationic
The r e l a t i v e l y
s e r v e s as t h e s t a r t i n g m a t e r i a l
stable
chloride
f o r t h e s e compounds.
A l l
129
the
four halides
have been r e p o r t e d
attempts t o repeat the preparation
by P a d l e y
.
Later
o f t h e pure i o d i d e were
125
unsuccessful
127
S^NgCl was f i r s t
together
S ^
p r e p a r e d b y Demarcay
and S C 1
2
2
i n CC1
(3S N
4
4
4
by h e a t i n g
+ 2S C1
2
2
• 4S N C1).
4
3
It
c a n b e p r e p a r e d by t h e a c t i o n o f SOClg o r a c e t y l
on
129
S.N.
o r by t h e r e a c t i o n o f S„N. w i t h d i s e l e n i u m d i c h l o r i d e
4 4
4 4
129
i n CC1
4
.
A l l other
sulphur
c h l o r i d e s as w e l l as t h e a d d u c t
S N . 4 H C 1 c a n be c o n v e r t e d t o S ^ C l .
4
4
When SgNgClg o r SgNgClg
i s h e a t e d w i t h SgClg i n CC1 , S NgCl i s formed.
4
chloride
4
Reaction o f
-37-
S„N C I
w i t h d i p h e n y l a c e t y l e n e o r c a r b o n monoxide a t about
40°C i n C C 1
4
g i v e s S^^Cl
a l s o be p r e p a r e d
a z i d e i n CC1.
4
it
32
i s assumed
S C1
4
t h e s i s p . 82
+
I t can
o
S i n c e t h e same r e a c t i o n g i v e s S_N a t 0 C,
4 4
.
t h a t S.N. i s t h e i n i t i a l
4 4
0
4
).
by t h e r e a c t i o n between S C I , and l i t h i u m
t o form S.N C I ( 4 L i N _ + 2 S C 1
0
3S N
(this
product
which r e a c t s w i t h
» S.N.
+
4 L i C l + 4N ;
0
2S C1 -»4S N C1).
2
2
4
3
S NgCl i s a yellow c r y s t a l l i n e s o l i d , s t a b l e i n dry a i r .
4
It
o
129
a t 170 C i n vacuo t o g i v e S N
.
decomposes
4
4
It is
i n s o l u b l e i n s o l v e n t s o f low d i e l e c t r i c c o n s t a n t s , b u t s o l u b l e
6
in
SOClg and f o r m i c a c i d
in
r e d needles
1 29
.
.
I t c a n be r e c r y s t a l l i s e d
S N C I decomposes
l
from S O C l g
s l o w l y i n b e n z e n e , CHC1 ,
O
O
129
acetone,
and a c e t i c a c i d by development o f a r e d c o l o u r
The c o u r s e
o f h y d r o l y s i s o f S N C I depends on t h e r e a c t i o n c o n d i t i o n s ,
W i t h i c e - c o l d sodium a c e t a t e s o l u t i o n , t h e i n i t i a l
0°C
.
i s t h e black S ^ g O H , w h e r e a s b l a c k
product a t
( S g N g O H ^ i s formed a t
129
room t e m p e r a t u r e
.
The h y d r o x i d e s
a r e probably
polymeric
and u n s t a b l e g i v i n g S N on s t a n d i n g .
The S N c a t i o n i s a p l a n a r s e v e n membered r i n g w i t h
4
ft
4
o
130,131
a l t e r n a t i n g S-N bonds and one S-S bond
N
N
three
-38-
The
evidence for pseudoaromaticity i n the r i n g i s
p r o v i d e d by
s t r u c t u r a l and
disagreement i n the
spectral studies.
l i t e r a t u r e over the extent
T h e r e i s however
of
it
delocalization,
132
Johnson e t a l
reports
equal,
S-N
of
thiotrithiazyl
the
bond l e n g t h s
t h a t , the planar
(1.
(S N
+
s t r u c t u r e and
short,
compared w i t h 1. 628 f«r
(S-N) )
) c a t i o n suggest that considerable
b o n d i n g o c c u r s i n t h i s r i n g s y s t e m and
sulphur d o r b i t a l s are used.
d e l o c a l i z a t i o n does not
s y s t e m and
the
system i n which
133
proposed
their results indicate
o c c u r o v e r t h e whole r i n g , t h e
the d i s u l p h i d e
however t h e e x i s t e n c e
Jt
Whereas B a i l e y e t a l
e l e c t r o n s y s t e m and
group a r e b e s t c o n s i d e r e d
separately,
d i s u l p h i d e group i s q u i t e l i k e l y .
S^NgF i s o b t a i n e d by t h e r e p l a c e m e n t of t h e c h l o r i d e
gas
that
delocalized
o f a c e r t a i n amount o f d e l o c a l i z a t i o n
S^NgCl, when a n h y d r o u s HF
rf"
the e l e c t r o n i c spectrum
i s consistent with a d e l o c a l i z e d , ten e l e c t r o n
a s i x o r e i g h t 'it
4
across
ion
in
i s a l l o w e d t o r e a c t w i t h S^N^Cl
88
i n a p o l y e t h y l e n e or t e f l o n t u b e
A convenient general
(S^gCl + H F —
method f o r t h e p r e p a r a t i o n
>
S
of
N
4
F
3
thiotrithiazyl
compounds c o n s i s t s i n t h e m e t a t h e s i s o f s o l u t i o n s o f t h e
i n anhydrous formic a c i d .
c o l o u r e d S N SCN,
and
S.N
.SbCl
An
+ HC1).
chloride
o r a n g e - y e l l o w bromide, b r o n z e
red-brown t e t r a p h e n y l
b o r a t e , S.N
6
have been made i n t h i s way .
With
,B(C_H )
nitric
-39-
a c i d and s u l p h u r i c
S N .HSO
O
acid, S N CI gives
respectively
.
S N ,N0. and
A novel preparation
of t h e
ft
S
bromide i s by t h e r e a c t i o n o f bromine on (HNS)^ ( 4
S N Br + NH Br)
4
3
5 1
4
+
3
3
S N C1 + N H — ,
4
3
3
4
c a n be a c h i e v e d by r e a c t i o n
. 6
o f S N C I w i t h a l u m i n i u m a z i d e o r ammonia .
4
H
4
.
Ring expansion of S N
3S N C1 + A 1 ( N )
N
» 3S N
3
4
S N NH C1
4
3
3
+ 3N + 3 N
4
+
S N NH
4
4
2
2
+
+ AlClg,
S N .
4
4
+
E X P E R I M E N T A L
-40-
PREPARATIONS
.
. , 14,15,16.18,19,23,26
Tetrasulphur t e t r a n i t n d e : -
A t h r e e - n e c k e d round-bottomed was
vessel.
T h i s was
used as the r e a c t i o n
f i t t e d w i t h a paddle s t i r r e r
neck and a gas i n l e t
tube t h r o u g h
one
700 ml o f c a r b a n t e t r a c h l o r i d e
25 ml o f d i s u l p h u r d i c h l o r i d e
of the s i d e
( d r i e d o v e r P^O-^o^
While s t i r r i n g
passed through
g r e e n l a y e r o f c h l o r i n e gas was
solution.
A f t e r about
passed through
and
were added
observed over
the s o l u t i o n as r a p i d l y as
possible
flask.
c o p i o u s w h i t e fumes were formed w h i c h
soon
formed
The c o l o u r t h e n changed t o a g r e y g r e e n , brown
f i n a l l y a f t e r about
t h r e e h o u r s t o a r e d d i s h brown o r
y e l l o w i s h brown s u s p e n s i o n .
The
f l o w o f ammonia was
then
stopped.
D u r i n g t h e p a s s a g e o f ammonia t h e l i q u i d
f l a s k was
m a i n t a i n e d t o a c o n s t a n t volume by o c c a s i o n a l l y
carbon t e t r a c h l o r i d e through
a funnel.
the
the apparatus
d i s a p p e a r e d and a t h i c k y e l l o w brown s u s p e n s i o n was
i n the f l a s k .
d
s t r e a m o f ammonia from a
w i t h o u t c a u s i n g m a t e r i a l t o s p l a s h from t h e
Initially
n
briskly
t h r e e q u a r t e r s o f an h o u r ,
immersed i n an i c e - b a t h and a f a s t
c y l i n d e r was
a
the s o l u t i o n u n t i l a
distinctly
was
t h e main
necks.
(sulphur monochloride)
to a o n e - l i t r e r e a c t i o n v e s s e l .
d r y c h l o r i n e gas was
through
i n the
adding
t h e t h i r d neck o f t h e f l a s k u s i n g
-41-
The
r e a c t i o n mixture
was f i l t e r e d
on a s i n t e r e d - g l a s s
f u n n e l and t h e s o l i d m a t e r i a l was s l u r r i e d w i t h about 500 ml
of water
X
f o r 10-15 m i n u t e s .
T h e p r e c i p i t a t e was s e p a r a t e d
by f i l t e r a t i o n and t h o r o u g h l y
air-dried
f o r a day o r two.
To remove S^NH, t h e d r i e d r e s i d u e was s h a k e n w i t h 150 ml
of e t h e r f o r t e n minutes i n a wide necked reagent
s o l u t i o n was d e c a n t e d
bottle.
The
o f f and t h e p r o c e s s was r e p e a t e d .
(This
p r o c e s s removes s o l i t t l e m a t e r i a l , t h e r e i s some doubt i f i t i s
necessary).
The y e l l o w o r y e l l o w i s h g r e e n
e x t r a c t e d w i t h dry benzene.
e x t r a c t i o n tube was u s e d
continued
yellow.
was
d r y r e s i d u e was
E i t h e r a S o x h l e t e x t r a c t o r or an
forthis.
The e x t r a c t i o n was
u n t i l t h e e l u a t e was c o l o u r l e s s o r f a i n t l y
orange
When a l l t h e S^N^ was e x t r a c t e d , t h e e x t r a c t i o n p o t
c o o l e d and p u r e t e t r a s u l p h u r t e t r a n i t r i d e c r y s t a l l i s e d
the s o l u t i o n a s orange-red
o f 12-14 g. o f S N
4
purification
4
or orange-yellow
needles.
(m.p. 178-179°) were o b t a i n e d .
from
Yields
Further
i f n e c e s s a r y may be e f f e c t e d by s u b l i m a t i o n i n h i g h
vacuum w i t h a b a t h
temperature
o f about
100°C.
14(b)
P r e c a u t i o n s f o r w o r k i n g w i t h S^N^ a r e a s f o l l o w s
S^N^ i t s e l f
should
c a n o n l y become d a n g e r o u s i n a d r y s t a t e , b u t one
take note of t h e f o l l o w i n g :
Do n o t work w i t h more t h a n
with a metal
lOg o f d r y S^N^.
Do n o t t o u c h i t
s p a t u l a , and do n o t s t o r e t h e d r y s u b s t a n c e
i nbottles
-42-
w i t h ground g l a s s s t o p p e r s i n o r d e r t o s a v e t h e
from b e i n g ground between t h e two
c a u s e s an e x p l o s i o n .
crystals
s u r f a c e s , which
While working with S N
usually
i n dry
n o r m a l p r e c a u t i o n s a r e s u f f i c i e n t , e.g. a p l a t e of
Phenylboron d i c h l o r i d e
Boron t r i c h l o r i d e
(PhBCl )
5
4
(
a
)
(
•
2
b
)
1
•
9
state
safety-glass.
1
( 5 . 2 1 4 g . , 0.453 m o l . ) was
added t o a
s u s p e n s i o n of t e t r a p h e n y l t i n ( 4 . 2 0 5 g . , ) i n dry m e t h y l e n e
( 1 0 m l ) a t -80°C.
t o between 0°C
The
and
The m i x t u r e was
allowed
5°C when a v i o l e n t
v o l a t i l e m a t e r i a l (methylene
dichloride
t o warm g r a d u a l l y
reaction
occurred.
d i c h l o r i d e c o n t a i n i n g some
o
boron t r i c h l o r i d e ) was
removed and
r e s i d u e gave a m i x t u r e
of phenylboron d i c h l o r i d e
and
phenyltin trichloride
d i c h l o r i d e was
purified
(Yield
90% based
4.2
g.,
t r a p p e d a t -80 C.
( b . p . 129-130°C).
by
The
( b . p . 65-70°C)
Phenylboron
s e v e r a l d i s t i l l a t i o n s under vacuo
on t h e e q u a t i o n , P h S n + 3 B C 1
4
3
>
3PhBCl„ + P h S C l _ ) .
n
D i p h e n y l mercury:
B.D.H. l a b o r a t o r y r e a g e n t was
from h o t
p u r i f i e d by
recrystallisation
chloroform.
p-Tolytin trichloride:
(C H S n C l
f
p-Bromotoluene (171 g,
t o magnesium ( 2 4 . 3 g.,
a h a l f hours.
The
/
)
5
2
(
a
)
'
(
b
)
O
1 m o l e ) i n e t h e r ( 1 0 0 m l ) was
added
1 g atom) i n e t h e r ( 5 0 0 m l ) d u r i n g one
r e a c t i o n m i x t u r e was
and
r e f l u x e d f o r 30 m i n u t e s
-43-
and
then allowed
to c o o l
t o room t e m p e r a t u r e .
Stannic
bromide ( 7 6 * 5 g., 0*175 m o l e s ) i n benzene was added t o t h e
r e a c t i o n mixture during
40 m i n u t e s and t h e n t h e r e a c t i o n m i x t u r e
was r e f l u x e d f o r two and a q u a r t e r h o u r s .
was c o o l e d
ice-water
The r e a c t i o n m i x t u r e
to room t e m p e r a t u r e and h y d r o l y s e d
by t h e a d d i t i o n o f
( 5 0 0 m l ) and i c e - c o l d 5% h y d r o c h l o r i c
After f i l t r a t i o n
the organic
a c i d (200 ml.)
l a y e r was s e p a r a t e d ,
d r i e d over
MgSO^, and s o l v e n t was removed under vacuum t o g i v e
t o l y t i n ( 7 1 g., 8 5 % ) , w h i c h was r e c r y s t a l l i s e d
p-Tolytin
tetra-p-
from benzene.
t r i c h l o r i d e was p r e p a r e d by t h e r e d i s t r i b u t i o n r e a c t i o n
of t e t r a - p - t o l y t i n w i t h
stannic chloride.
The two components i n
1:1 r a t i o w e r e m i x e d a t room t e m p e r a t u r e and a l l o w e d
to stand
f o r 2-3 h o u r s .
S t a n n i c c h l o r i d e (B.D.H. s t a n d a r d
p u r i f i e d by d i s t i l l a t i o n
laboratory reagent)
under d r y n i t r o g e n
was
a t m o s p h e r e o r under v a c u o
S t a n n i c bromide (B.D.H.) was p u r i f i e d by s u b l i m a t i o n
under vacuum
a t room t e m p e r a t u r e .
Stannic
hot
iodide
(B.D.H.) was p u r i f i e d by r e c r y s t a l l i s a t i o n
from
chloroform.
Stannic
fluoride (Alfa Inorganics
without f u r t h e r
Titanium
vacuo.
I n c . ) was u s e d
directly
purification.
t e t r a c h l o r i d e (B.D.H.) was p u r i f i e d by d i s t i l l a t i o n
under
-44-
Titanium
tetrabromide
(Alfa Inorganics Inc.) purified
by
s u b l i m a t i o n under vacuum a t 3 0 - 4 0 ° C
Titanium
tetraiodide
( A l f a I n o r g a n i c s I n c . ) was p u r i f i e d
by
s u b l i m a t i o n under vacuum a t 140-160°C.
Titanium
further
tetrafluoride
tetrachloride
to remove any t r a c e s
recrystallisation
Zirconium
(B.D.H.) was f i r s t
of moisture
and then p u r i f i e d
SOC^
by
t e t r a f l u o r i d e ( A l f a I n o r g a n i c s Inc.) was u s e d
without
purification.
( A l f a I n o r g a n i c s I n c . ) was u s e d
without
purification.
Aluminium t r i c h l o r i d e was p u r i f i e d
nitrogen
refluxed with
from S O C ^ -
Hafnium t e t r a c h l o r i d e
further
without
purification.
Zirconium
further
( A l f a I n o r g a n i c s I n c . ) was u s e d
by s u b l i m a t i o n i n a d r y
atmosphere.
Aluminium t r i b r o m i d e ( H o p k i n and W i l l i a m s ) was p u r i f i e d
by
s u b l i m a t i o n under v a c u o .
Gallium
t r i c h l o r i d e was p u r c h a s e d
without
further
from K o c h - L i g h t
purification.
I n d i u m t r i c h l o r i d e , InCl^-H^O was p u r c h a s e d
was removed by r e f l u x i n g
Thallium
L t d . , and u s e d
with
thionyl
t r i c h l o r i d e was p r e p a r e d
from B.D.H. and w a t e r
chloride.
from t h a l l o u s
chloride (Alfa
( I n o r g a n i c s I n c . ) and c h l o r i n e i n d r y a c e t o n i t r i l e ,
(pp.67-68).
-45-
S e l e n i u m t e t r a c h l o r i d e was
prepared
by
t h e r e a c t i o n between
36
s e l e n i u m and c h l o r i n e i n dry C C l ^
.
Pure selenium
was
suspended i n C C l ^ i n a two-necked round-bottomed f l a s k
dry c h l o r i n e was
then i n t r o d u c e d .
The Se soon d i s s o l v e d and
t h e s o l u t i o n t u r n e d brown ( f o r m a t i o n o f Se^Cl^);
t i m e S e C l ^ s e p a r a t e d a s a y e l l o w - w h i t e powder.
filtered
was
i n absence
p u r i f i e d by
o f m o i s t u r e and d r i e d by
o
gas.
Selenium
t e t r a f l u o r i d e was
by a n a l o g y
f l u o r i n e and
prepared
cone and
u s e d was
suction.
(Se C I
SeCl^
+ 5F—»SeF
£t
£
c o n s t r u c t e d from P y r e x ,
s o c k e t and b a l l
three-necked
was
w i t h t h e p u b l i s h e d p r e p a r a t i o n v i z from
diselenium dichloride
apparatus
SeCl^
by t h e r e a c t i o n between C 1 F
£
The
a f t e r some
s u b l i m a t i o n a t 196 C i n t h e a t m o s p h e r e o f dry
chlorine
and S e C I
and
socket j o i n t s .
round-bottomed f l a s k
c h l o r i n e - t r i f l u o r i d e and
+
2FC1)
Q
and
employed
I t c o n s i s t e d of a 250
for mixing
dry n i t r o g e n
a 100 ml two-necked r e a c t i o n
stopcocks.
flask
bath.
T h i s was
Each
c a p a b l e o f i s o l a t i o n by means o f
A l l j o i n t s were g r e a s e d w i t h F l u o r o l u b e
Diselenium d i c h l o r i d e
ml
and
f o l l o w e d by a t r a i n of t r a p s a t -196°C f o r p u r i f i c a t i o n .
s e c t i o n o f t h e a p p a r a t u s was
(10 g.) was
commencement of f l u o r i n a t i o n .
d r y n i t r o g e n f o r about a n h o u r .
'W g r e a s e .
c o o l e d i n an i c e s a l t
found t o be n e c e s s a r y t o p r e v e n t
The a p p a r a t u s was
4 7
i g n i t i o n a t the
flushed with
C h l o r i n e t r i f l u o r i d e from
the
^
&
-46-
cylinder
h a l f an
was
d i l u t e d w i t h dry
hour and
increased
reaction
then the
n i t r o g e n was
passed slowly
r a t e of c h l o r i n e
u n t i l only a c o l o u r l e s s
vessel.
and
the
The
p r o d u c t was
The
a p p a r a t u s was
chlorine
flushed
t r i f l u o r i d e supply
l i q u i d remained i n
t r i f l u o r i d e was
w i t h dry
t h e n p u r i f i e d by
for
trap
the
switched
off
n i t r o g e n f o r about an
to t r a p
hour.
d i s t i l l a t i o n i n vacuo.
47(b)
Tellurium
tetrafluoride
The
r e a c t i o n employed f o r t h e p r e p a r a t i o n o f
was
that
2SeF.
of s e l e n i u m t e t r a f l u o r i d e and
> TeF
+ 2SeOF ) .
tellurium
first
of which
c a r r i e d the
The
m i x t u r e was
the
t e m p e r a t u r e a p p r o a c h e d 80°C t h e r e was
the
tellurium
u n t i l the
and
was
slowly
h e a t e d by
d i o x i d e (TeO
The
evacuated t r a i n of
dry
tellurium
dioxide.
t e m p e r a t u r e was
distilled
i n t o another bulb.
The
from t h e r e s i d u e by k e e p i n g i t a t
p u r i f i e d by s u b l i m a t i o n i n v a c u o .
and
raised
vapour p r e s s u r e
t e m p e r a t u r e f o r about 15 m i n u t e s ,
s e l e n i u m t e t r a f l u o r i d e and
As
a vigorous reaction
l i q u i d began t o r e f l u x under i t s own
which the
+
distilled
means of a w a t e r - b a t h .
dioxide dissolved.
kept a t that
tetrafluoride
S e l e n i u m t e t r a f l u o r i d e was
from a s t o r a g e b u l b i n t o a c a r e f u l l y d r i e d ,
b u l b s , the
tellurium
after
selenium oxyfluoride
were
l a s t t r a c e s b e i n g removed
o
100 C i n v a c u o .
T
e
F
w
a
s
4
36
Tellurium
tetraiodide
:
T
e
I
w
4
a
s
p r e p a r e d by
the
reaction
acid
between t e l l u r i c / a n d h y d r o g e n i o d i d e (Te(0H) +6HI-»TeI +1 +6H
fl
0).
-47-
A very concentrated
telluric
a c i d s o l u t i o n i s mixed w i t h
slightly
more t h a n t h e s t o i c h i o m e t r i c q u a n t i t y of fuming h y d r i o d i c a c i d .
A heavy, g r e y p r e c i p i t a t e of T e l ^ i m m e d i a t e l y
was
suction f i l t e r e d
several
was
on a f r i t t e d g l a s s f i l t e r
t i m e s w i t h p u r e C C l ^ to remove i o d i n e .
washed
product
a n a l y t i c a l l y p u r e (Found: I = 80'3%; t h e o r y I =
79*93).
purified
purchased
from A l f a I n o r g a n i c s I n c .
by s u b l i m a t i o n i n v a c u o .
Niobium p e n t a f l u o r i d e ( K o c h - L i g h t
was
and
It
The
Niobium p e n t a c h l o r i d e was
and
separated.
used w i t h o u t
standard laboratory
reagent)
further purification.
T a n t a l u m p e n t a c h l o r i d e and T a n t a l u m p e n t a f l u o r i d e
(Koch-Light
s t a n d a r d l a b o r a t o r y r e a g e n t s ) were u s e d w i t h o u t
further purification.
Vanadium o x y t r i c h l o r i d e and WOCl^ were p r e p a r e d
by
t h e methods
36
d e s c r i b e d by
Brauer.
T u n g s t e n h e x a c h l o r i d e was
purhcased
from K o c h - L i g h t
purification.
120
T u n g s t e n hexabromide
WC1, + 2BBr
» WBr, + 2BCl„ 2*1 g. o f WCl, was
o
j
o
3
b
and u s e d
without
further
i n a two-necked round-bottomed f l a s k and
t r i b r o m i d e (B.D.H.) was
s l o w l y warmed to 0°C
occurred.
f l a s k was
water
The
e x c e s s o f boron
condensed on i t a t -196
reaction flask
allowed
C.
The
when a v i g o r o u s r e a c t i o n
to s t a n d i n a b a t h
(10°C) f o r about an hour and
were removed by c o n d e n s i n g
placed
of c o l d
t h e e x c e s s o f boron h a l i d e s
a t -196°C.
The
tungsten
hexabromide
-48-
was
o b t a i n e d a s a b l a c k powder (Found: Br = 72.18; t h e o r y : B r =
Trithiazyl
The
trichloride
(S^NgCl
p r e p a r a t i o n was
^
carried
out
i n the absence
A Schlenk
o r a two-necked round bottomed f l a s k was
apparatus
f o r the p r e p a r a t i o n .
was
p l a c e d i n a S c h l e n k and
c h l o r i d e ( 2 5 m l ) was
was
t h e s t i r r i n g was
rubber
used
( p . 50
The
as
the
(5
mixture
stirrer.
The
s l o w l y changed t o r e d a f t e r
continued
f o r 16-24
1-2
hours, u n t i l
( t h e e x i t gas was
(decomposes w i t h S O g C l g ) or p l a s t i c
g.)
) sulphuryl
reaction
using a teflon
e v o l u t i o n of s u l p h u r d i o x i d e c e a s e d
through
purified
added t o t h e S^N^.
s t i r r e d a t room t e m p e r a t u r e
h o u r s , and
of m o i s t u r e .
Tetrasulphur tetranitride
freshly
c o l o u r of the r e a c t i o n mixture
72.30).
the
l e d away
tubing
into
a fuming c h a m b e r ) .
The
p a l e - y e l l o w - w h i t e powdery S„N C I : w h i c h s e t t l e d
o
was
f i l t e r e d from t h e s u p e r n a t e n t
chloride
(5-10 ml) d r i e d
recrystallisation
The
i f necessary purified
r e d l i q u i d was
by pumping and
f u r t h e r y e l l o w - w h i t e S ^ N ^ C l ^ was
recrystallised
from dry C C l ^ .
was
The
out
O
r e d l i q u i d , washed w i t h s u l p h u r y l
i n v a c u o , and
from d r y C C l ^ .
o
evaporated
obtained
t o t a l y i e l d before
by
and
crystallisation
quantitative.
The
trithiazyl
trichloride
when f r e s h l y
crystallised
was
a pale-yellow-white c r y s t a l l i n e
s o l i d , w h i c h changed t o y e l l o w
standing for s e v e r a l days.
m.p. o f t h e f i r s t
The
after
batch of S N C I
-49-
was
90-91°C, w h e r e a s t h e SgNgClg
recrystallised
from SOgClg
m e l t e d a t 93-94°C.
S N CI
•3
O
i s s o l u b l e i n carbon t e t r a c h l o r i d e (1 g i n 2 5
C C l ^ ) , benaene, c h l o r o f o r m , c a r b o n d i s u l p h i d e ,
sulphury1 c h l o r i d e .
When r e c r y s t a l l i s e d
c r y s t a l l i s e s as yellow-white
flakes.
in g l a s s containers with a i r - t i g h t
with
D r y i n g and
S„N_C1
should
be
stored
J
or
glass
teflon sleeves.
p u r i f i c a t i o n o f s o l v e n t s and
by A . W e i s s b e r g e r " ^ ^ ^ .
were d r i e d over sodium w i r e ,
sodium and
o
benzene i t
polyethylene stoppers
Most o f t h e s o l v e n t s were d r i e d and
described
thionyl chloride,and
from hot
O
stoppers
ml
O
other
liquid
p u r i f i e d by
materials
t h e methods
Non-halogenated s o l v e n ts
redistilled
i f necessary
from
s t o r e d i n a t h r e e - n e c k e d f l a s k o v e r c l e a n sodium w i r e ,
in a nitrogen
atmosphere.
Q u a n t i t i e s o f s o l v e n t s were removed
by u s i n g a long n e e d l e d s y r i n g e w h i l s t dry
n i t r o g e n was
flushed
through the v e s s e l .
104
Carbon t e t r a c h l o r i d e
o v e r ? 2 ^ g f o r a day or two
C
distillation
under dry
C
1
4
( A n a l a R g r a d e ) was d r i e d on s t a n d i n g
and t h e n i f n e c e s s a r y p u r i f i e d by
nitrogen
atmosphere.
36(a)
Carbon d i s u l p h i d e
C o m m e r c i a l c a r b o n d i s u l p h i d e was
w i t h mercury f o r 4-6
and
fractionally
agitated
hours, d r i e d w i t h phosphorus pentoxide
distilled
i n vacuum a v o i d i n g
a l l greased
joints.
-50-
Methylene d i c h l o r i d e
54
C H ^ C l ^ was
refluxed
over phosphorus p e n t o x i d e , d i s t i l l e d ,
nitrogen
and
f o r 3-4
stored
hours
in a
dry
atmosphere.
36
Sulphury1 Chloride
was
S O ^ C l g (B.D.H. s t a n d a r d
fractionally distilled
laboratory
t h r o u g h a t w e l v e i n c h column p a c k e d
w i t h g l a s s h e l i c e s , connected to a r e f l u x d i s t i l l a t i o n
equipped w i t h a c a l c i u m
reagent)
chloride drying
tube.
The
c o l o u r l e s s f r a c t i o n b o i l i n g between 69-70°C was
head
middle
p u r e SO
CI
.
119
Thionyl
the
chloride
Triphenyl
thionyl chloride
minutes.
The
ml)
was
(1 l i t r e ) w i t h v i g o r o u s s t i r r i n g
m i x t u r e was
m i d d l e f r a c t i o n was
p h o s p h i t e (160
f r a c t i o n a t e d and
c o l l e c t e d and
the
added
for
to
30
'water w h i t e '
stored.
36(a)
Nitriles
Acetonitrile, propionitrile,
isobutyronxtrile
and
t e t e r t i a r y b u t y 1 c y a n i d e were d r i e d o v e r p h o s p h o r u s p e n t o x i d e
and
p u r i f i e d by
a
Epoxides * ^ ^
distillation
w e r e vacuum
fractional distillation.
Epichlorohydrin
(b.p.
116°C.)
was
p u r i f i e d by f r a c t i o n a l
Ethylene
o x i d e and
epibromohydrin
distilled.
Experimental Techniques
A l l m a n i p u l a t i o n s o f a i r and
were c a r r i e d out
The
i n the g l o v e b o x shown i n f i g u r e
overleaf.
Drybox
This consisted
and
m o i s t u r e s e n s i t i v e compounds
24
inches
o f a s t e e l box
39
inches
deep w i t h a p e r s p e x r o o f and
l o n g , 29
f r o n t , and
inches
high
w i t h two
front
r
ST3
J
4*
.j
4a
11
i.
..v
i
r
. i
.1
1
J
1
1
1
0
u:
0
Tl
Ik
•I
t UJ
o ©
—r3s
2V
JO
III
s
u.
LU
-J
i
o
UJ
CO
Ul
(9
Ul
(0
-51-
p o r t s used f o r armholes.
Ltd.,
I t was o b t a i n e d from L i n t o t t E n g i n e e r i n g
Horsham, Sussex (MK X I G l o v e b o x ) .
The perspex windows
were f i t t e d w i t h rubber a i r t i g h t s e a l s ; 'Charco, B u t a - s o l , 5B
3032' ( o r neoprene) arm-length g l o v e s were used on t h e f r o n t
parts.
A t one s i d e o f t h e box was a c y l i n d r i c a l t r a n s f e r tube ( ' p o s t i n g
p o r t ' ) 18 inches l o n g and 9 inches d i a m e t e r , which opened i n t o
the drybox by means o f a s c r e w - i n p a r t and which s i m i l a r l y opened
t o t h e a i r a t t h e o t h e r end. A s t r i p - l i g h t was mounted o u t s i d e
the perspex r o o f and e l e c t r i c i t y was c a r r i e d i n t o t h e box which
c o n t a i n e d a r e c i r c u l a t i n g pump.
Behind t h e t r a n s f e r tube were
f o u r 1 cm. diameter tubes l e a d i n g t h r o u g h t h e s i d e o f t h e
apparatus and c l o s e d i n s i d e and o u t by 4 mm. g l a s s h i g h vacuum
t a p s , w h i l s t t h e f l o o r was covered w i t h a sheet o f b l a c k p l a s t i c
material or
aluminium k i t c h e n
foil.
The n i t r o g e n atmosphere i n t h e d r y box was k e p t f r e e from
oxygen and m o i s t u r e i n t h e f o l l o w i n g way.
The pump which c o u l d
c o m p l e t e l y r e c y c l e t h e atmosphere i n t h e box i n t e n h o u r s ,
passed n i t r o g e n o u t t h r o u g h a 4 mm, t a p , t h r o u g h a t r a p 18 inches
deep c o o l e d i n l i q u i d a i r , over copper w i r e packed i n two s i l i c a
o
towers a t 400 C, t h r o u g h a second t r a p s i m i l a r l y c o o l e d , and back
t h r o u g h another 4 mm. t a p i n t o t h e box.
T h i s c i r c u l a t i o n was
m a i n t a i n e d whenever t h e d r y box was n o t b e i n g used f o r e x p e r i m e n t s .
-52-
Copper towers and l i q u i d a i r t r a p s were connected t o t h e drybox
by P.V.C. and s i l i c o n e t u b i n g and n o r m a l l y t h e p r e s s u r e i n t h e
box was m a i n t a i n e d s l i g h t l y above a t m o s p h e r i c .
the
N i t r o g e n from
bench supply c o u l d be i n t r o d u c e d i n t o t h e system v i a t h e copper
towers and l i q u i d a i r c o o l e d t r a p s as shown i n t h e f i g u r e .
A l l t h e apparatus i n t r o d u c e d i n t o t h e drybox was
first
p l a c e d i n the t r a n s f e r tube which had an i n l e t connected t o t h e
n i t r o g e n system o f t h e drybox,and n i t r o g e n f r o m t h e bench supply
was
f l u s h e d t h r o u g h v i a t h e copper towers and l i q u i d a i r t r a p s
and passed out o f t h e t r a n s f e r chamber v i a a gas b u b b l e r i n t o
the
air.
When t h e t r a n s f e r tube had been purged f o r a t l e a s t
one
hour t h e apparatus c o u l d be moved i n t o t h e drybox.
Analyses:
Analyses were performed by Messrs. R.Coult and T.Holmes
o f t h i s department and by D r s . W e i l e r and S t r a u s s o f the M i c r o a n a l y t i c a l l a b o r a t o r y , Oxford.
M o l e c u l a r Weights:
Mol. w t . d e t e r m i n a t i o n s were c a r r i e d o u t e i t h e r u s i n g a
Mechro.labvapour p r e s s u r e Osmometer, model 301A
or t h e c r y o s c o p i c
t e c h n i q u e u s u a l l y i n benzene adapted t o f a c i l i t a t e t h e use o f a i r
and m o i s t u r e s e n s i t i v e compounds.
-53-
Mass s p e c t r a :
Mass s p e c t r a were o b t a i n e d w i t h an A.E.I, (MS9) mass
s p e c t r o m e t e r on samples mounted on an i n e r t ceramic and
i n t r o d u c e d on a d i r e c t i n s e r t i o n p r o b e .
Infrared
Spectra:
I n f r a r e d s p e c t r a under n i t r o g e n were recorded
on Grubh-
1
Parsons GS2A o r Spectromaster (4000-400 cm ) and DM2/DB3(475-200 cm
prism
grating
spectrophotometers.
Spectra i n t h e potassium bromide r e g i o n were o b t a i n e d
e i t h e r as t h i n l i q u i d f i l m s ( i n t h e case o f low m e l t i n g compounds)
or as N u j o l m u l l s , between KBr p l a t e s .
For s p e c t r a i n t h e caesium i o d i d e r e g i o n , t h e t h i n
f i l m s o r m u l l s were supported
liquid
between two sheets o f one t e n t h
mm. t h i c k p o l y e t h y l e n e clamped i n a c e l l ( N u j o l c e l l ) t o g i v e an
a i r - t i g h t seal.
Reactions
Most o f t h e r e a c t i o n s were c a r r i e d o u t i n a Schlenk o r
i n a two-necked round-bottomed f l a s k i n an atmosphere o f d r y
nitrogen.
R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e and m e t a l h a l i d e s :
T i n tetrabromide
SnBr^ (1.2 g.) was d i s s o l v e d i n d r y hexane o r heptane ( 4 0 m l )
a t room t e m p e r a t u r e and S.N. ( 1 . 0 g.) was added t o t h e s o l u t i o n .
1
)
-54-
The r e a c t i o n m i x t u r e was s t i r r e d f o r 48-60 hours.
The
r e a c t i o n was slow and no immediate c o l o u r change was
observed.
A f t e r ^12-14 h o u r s , t h e c o l o u r o f t h e s o l u t i o n t u r n e d r e d d i s h
brown, f i n a l l y a deep brown p r e c i p i t a t e was o b t a i n e d , and no
f u r t h e r change i n t h e c o l o u r o f t h e p r o d u c t was
a f t e r about 48 h o u r s .
The p r e c i p i t a t e was f i l t e r e d ,
i n hexane (20 m l ) and d r i e d i n vacuo.
CC1 , CH C1 , E t 0 , CS .
4
2
2
observed
2
2
washed
The adduct i s i n s o l u b l e i n
F»und: S= 31.8; N.=13.65; Br =39.0.
S n B r ^ S . N . r e q u i r e s : S =31.73; N =13.65; Br =39.61%.
4
4 4
198-200°C ( d e c o m p o s i t i o n ) .
The compound g r a d u a l l y changed t o
a y e l l o w p r o d u c t upon exposure t o a i r .
the
M.P.
The i n f r a r e d spectrum o f
sample exposed t o a i r a f t e r s e v e r a l days (30-40) was s i m i l a r
t o t h e i . r . spectrum o f S^N^, w i t h a d d i t i o n a l peaks a t 1400 cm
3194 cm
1
1
,
p r o b a b l y due t o t h e h y d r o l y s i s p r o d u c t o f t h e h a l i d e .
52,53
Tin
tetrachloride
T e t r a s u l p h u r t e t r a n i t r i d e (0.92 g ) was d i s s o l v e d i n CC1
4
(50 m l ) and t i n t e t r a c h l o r i d e (1.3 g ) added dropwise a t room
temperature.
A deep r e d p r e c i p i t a t e o f S n C l . 2 S N
immediately.
The compound was f i l t e r e d , and p u r i f i e d by washing
i n CC1
4
4
and pumped dry a t room t e m p e r a t u r e .
4
M.P.
C I =22.54; S n C l . 2 S N
4
4
4
r e q u i r e s : C I =22.57.
was
formed
200°C (decomp.)
The adduct i s i n s o l u b l e i n CC1 , C f ^ C l g , EtgO, CS .
4
4
2
Found,
-55-
Tin tetrafluoride:
A t t e m p t s were made t o p r e p a r e t h e adduct o f SnF^.
I n one
experiment t i n t e t r a f l u o r i d e (1.0 g ) was suspended i n 30 ml o f
a c e t o n i t r i l e and S^N^ (1.0 g ) was added, t h e s o l u t i o n was
r e f l u x e d f o r 24 h o u r s , w h i l e i n an another e x p e r i m e n t , SnF^
(0.7 g ) was h e l d i n 40 ml o f d r y T.H.F. and S N
4
added, t h e m i x t u r e was r e f l u x e d f o r 14 h o u r s .
o r o t h e r change i n appearance was n o t e d .
4
(0.7 g ) was
No c o l o u r change
The i . r . s p e c t r a o f
t h e p r o d u c t s showed o n l y unchanged s t a r t i n g m a t e r i a l s .
Tin tetraiodide:
( a ) S n l ^ (1.9 g ) was d i s s o l v e d i n d r y c h l o r o f o r m (40 m l )
and S^N^ ( 1 . 1 g ) i n 25 ml o f h o t d r y c h l o r o f o r m was added i n p o r t i o n s ,
no immediate r e a c t i o n was observed.
24 h o u r s .
The s o l u t i o n was s t i r r e d f o r
No change i n appearance was observed; t h e spectrum o f
t h e evaporated s o l u t i o n showed o n l y S^N^.
(b) S n l
4
(1.5 g ) was d i s s o l v e d i n CSg (30 m l ) and
i n CSg (40 m l ) was added a t room t e m p e r a t u r e .
(0.9 g )
The s o l u t i o n was
s t i r r e d f o r 24 hours and c o n c e n t r a t e d t o a s m a l l volume.
No
r e a c t i o n was found t o t a k e p l a c e .
Stannous c h l o r i d e
T e t r a s u l p h u r t e t r a n i t r i d e (1.0 g ) was suspended i n e t h e r (40 m l )
and SnClg ( 1 . 0 g ) added a t room t e m p e r a t u r e .
was s t i r r e d f o r 48 h o u r s .
I
The r e a c t i o n m i x t u r e
No obvious r e a c t i o n was observed.
-56Germanium t e t r a c h l o r i d e
F o l l o w i n g a t t e m p t s were made t o s t u d y t h e r e a c t i o n between
GeCl„ and S.N..
4
4 4
( a ) T e t r a s u l p h u r t e t r a n i t r i d e ( 1 . 2 g ) was suspended i n CCl^
and GeCl^ ( 2 m l ) added a t room t e m p e r a t u r e .
s t i r r e d f o r 24 h o u r s .
(b) G e C l
4
The s o l u t i o n was
No r e a c t i o n was found t o t a k e p l a c e .
(10 m l ) was added t o S^N^ (1.0 g ) a t room t e m p e r a t u r e
and t h e r e a c t i o n m i x t u r e was s t i r r e d f o r 30 h o u r s .
Since t h e r e
was no obvious r e a c t i o n , t h e r e a c t i o n temperature was r a i s e d t o
75°C and s t i r r i n g was c o n t i n u e d f o r 4 h o u r s .
or o t h e r change i n appearance was n o t e d .
No c o l o u r change
The i n f r a r e d
spectrum
of t h e evaporated s o l u t i o n showed o n l y unchanged s t a r t i n g m a t e r i a l s .
Silicon
tetrachloride
T e t r a s u l p h u r t e t r a n i t r i d e ( 1 . 0 g ) was t a k e n i n a Schlenk and
S i C l ^ ( 1 0 m l ) added a t room t e m p e r a t u r e .
s t i r r e d f o r 48 h o u r s .
The r e a c t i o n m i x t u r e was
The i n f r a r e d spectrum o f t h e evaporated
s o l u t i o n showed o n l y unchanged s t a r t i n g m a t e r i a l s .
Selenium t e t r a c h l o r i d e
SeCl^ ( 1 . 1 g) was suspended i n benzene or t o l u e n e (20 m l )
and t e t r a s u l p h u r t e t r a n i t r i d e added t o t h e s o l u t i o n a t 0°C.
s o l u t i o n was s t i r r e d f o r 24 h o u r s .
The
The r e a c t i o n was v i g o r o u s
i n i t i a l l y and a b r i g h t y e l l o w p r e c i p i t a t e was o b t a i n e d a t t h e end o f
the
r e a c t i o n a f t e r 24 h o u r s .
The p r e c i p i t a t e was f i l t e r e d ,
-57washed i n benzene (15 m l ) and d r i e d i n vacuo.
Found: Se=20.60,
S=28.71, N=13.88, Cl=34.61; SeCl .S N r e q u i r e s ; Se=19.54;
S=31.60, N=13.83, Cl=34.99.
M.P. 127-129°C.
The compound
i s i n s o l u b l e i n CCl^, CHCl^.
I t t u r n s r e d upon exposure t o a i r .
Tellurium tetrachloride
4
T e t r a s u l p h u r t e t r a n i t r i d e (0.46 g) was d i s s o l v e d
(20 m l ) and t e l l u r i u m t e t r a c h l o r i d e (0.73 g)
added a t room t e m p e r a t u r e .
The compound was washed i n t o l u e n e
d r i e d by pumping a t room t e m p e r a t u r e .
N =12.45; C l = 31.60; TeCl .S N
4
Cl» 31.25.
M.P.
140°C.
CH C1 , CS , Et 0.
0
i n t o l u e n e (10 m l )
An immediate deep r e d p r e c i p i t a t e
was formed and f i l t e r e d o f f .
and
i n toluene
Found: S= 28.75,
r e q u i r e s : Sb 28.26; N = 12.35;
The compound
i s i n s o l u b l e i n CC1 ,
4
The adduct changes t o a y e l l o w p r o d u c t
g i v i n g p r o b a b l y t e t r a s u l p h u r t e t r a n i t r i d e and t h e h y d r o l y s i s
product of the h a l i d e .
Tellurium
tetrafluoride
The r e a c t i o n was c a r r i e d o u t i n a two-necked 100 ml r o u n d bottomed f l a s k .
T e l l u r i u m t e t r a f l u o r i d e (0.4 g ) was
dissolved
i n d r y a c e t o n i t r i l e (45 m l ) a t room t e m p e r a t u r e and t e t r a s u l p h u r
t e t r a n i t r i d e (0.36 g ) added t o t h e above s o l u t i o n .
c o l o u r change was observed.
and
No immediate
The s o l u t i o n was r e f l u x e d f o r 72 hours
a deep r e d s o l u t i o n was o b t a i n e d .
The s o l u t i o n was c o n c e n t r a t e d
t o a s m a l l volume (10 m l ) and a b r i g h t deep r e d p r e c i p i t a t e was
-58-
obtained.
and
The p r e c i p i t a t e was f i l t e r e d , washed i n
d r i e d i n vacuo.
i n colour.
92°C.
acetonitrile
When dry the compound was brownish-orange
Found: N=15.24, T e F . S N
4
4
r e q u i r e s , N=14.44.
4
M.P.
There was i n s u f f i c i e n t sample f o r f u r t h e r a n a l y s i s .
The
adduct changes t o a y e l l o w compound upon exposure t o a i r .
Tellurium
Tel
tetraiodide
(1.0 g ) and t e t r a s u l p h u r t e t r a n i t r i d e
4
(0.29
g)
i n e t h e r (40 ml) were shaken t o g e t h e r f o r about a week.
r e a c t i o n was found t o t a k e p l a c e , p r o b a b l y due t o the
of t e l l u r i u m t e t r a i o d i d e i n e t h e r .
No
insolubility
Methylene d i c h l o r i d e was
a l s o used as a s o l v e n t t o study t h e r e a c t i o n , b u t no r e a c t i o n was
observed.
Titanium tetrabromide
TiBr
4
(2.0 g ) was d i s s o l v e d
i n 30 ml o f dry methylene
d i c h l o r i d e ( o r o-dichlorobenzene o r e t h e r ) and t e t r a s u l p h u r
tetranitride
(0.67
g ) added a t room t e m p e r a t u r e .
a r e d d i s h brown p r e c i p i t a t e was formed.
f o r 10 h o u r s .
Immediately
The s o l u t i o n was s t i r r e d
The deep brown p r e c i p i t a t e was f i l t e r e d , washed
i n methylene d i c h l o r i d e and pumped d r y a t room t e m p e r a t u r e .
Found: S=22.1, N=10.34, Br=59.1; T i B r
Br=57.34.
M.P. 138°C.
4 >
S N
4
4
requires;
S=23.2, N=10.15,
I t i s i n s o l u b l e i n CC1 , CHgClg.
4
exposed t o a i r , i t t u r n s y e l l o w g i v i n g p r o b a b l y t e t r a s u l p h u r
and
the h y d r o l y s i s
p r o d u c t o f the
halide.
When
tetranitride
-59-
52,53
Titanium tetrachloride
T e t r a s u l p h u r t e t r a n i t r i d e (0.92 g ) was d i s s o l v e d i n
carbon t e t r a c h l o r i d e ( 4 0 m l ) and t i t a n i u m t e t r a c h l o r i d e ( 0 . 8 1 g )
added a t room t e m p e r a t u r e .
An immediate
yellow-orange
p r e c i p i t a t e o f S^N^.TiCl^ was o b t a i n e d and f i l t e r e d from t h e
solution.
The p r o d u c t was washed i n CCl^ and pumped d r y .
M.P. 135° (decomp.)
I t i s insoluble i n CC1
4>
Cll^Clg.
Titanium t e t r a f l u o r i d e
A t t e m p t s t o p r e p a r e t h e adduct o f T i F ^ u s i n g t h e s o l v e n t s
a c e t o n i t r i l e , T.H.F., CH C I
were u n s u c c e s s f u l .
Methylene
d i c h l o r i d e was found t o be t h e most s u i t a b l e s o l v e n t .
TiF
4
( i )
( 1 . 0 g ) was r e f l u x e d w i t h 30 ml o f d r y a c e t o n i t r i l e f o r
was
24 hours and f i l t e r e d , t o t h e f i l t r a t e added t e t r a s u l p h u r
t e t r a n i t r i d e (0.2 g ) i n a c e t o n i t r i l e ( 2 0 m l ) a t room t e m p e r a t u r e .
The s o l u t i o n was s t i r r e d f o r 12 h o u r s .
of
The i n f r a r e d
spectrum
t h e evaporated p r o d u c t showed o n l y unchanged s t a r t i n g m a t e r i a l s .
(ii) TiF
( 1 . 0 g ) was suspended i n a c e t o n i t r i l e and S N
4
4
(0.2 g ) added t o t h e s o l u t i o n .
4
The r e a c t i o n m i x t u r e was r e f l u x e d
o
for
48 hours a t 92 C.
( i i i ) TiF
4
No obvious r e a c t i o n was observed.
( 1 . 1 g ) was r e f l u x e d w i t h T.H.F. ( 7 0 m l ) and t e t r a s u l p h u r
t e t r a n i t r i d e (0.2 g ) added a t room t e m p e r a t u r e .
was s t i r r e d f o r 12 h o u r s .
The s o l u t i o n
No r e a c t i o n was found t o t a k e p l a c e .
*60( i v ) T i F . (1.5 e ) was
susDended
i n methylene d i c h l o r i d e and
tetrasulphur
tetranitride
No
r e a c t i o n was observed.
immediate
s t i r r e d f o r 48 h o u r s .
(0.75 g ) added a t room t e m p e r a t u r e .
The r e a c t i o n m i x t u r e was
A deep r e d p r e c i p i t a t e was s l o w l y formed.
The compound was f i l t e r e d , washed i n CHgClg and pumped d r y a t
room t e m p e r a t u r e .
When d r y t h e adduct was orange i n c o l o u r .
Found: S=17.90, N=7.81, F=46.60; S ^ T i F ^ r e q u i r e s : S=18.83,
N=8.24, F=44.70, M.P.
i n CH C I , CS .
decomposed above 120°C.
I ti s insoluble
The adduct changes t o a y e l l o w p r o d u c t upon
exposure t o a i r .
Titanium t e t r a i o d i d e
Til
( 1 . 0 g ) was d i s s o l v e d i n 40 ml o f d r y CC1
4
or CSg) and t e t r a s u l p h u r t e t r a n i t r i d e
temperature.
CC1 and d r i e d i n vacuo.
4
4 #
S N
4
(0.25 g ) added a t room
The compound was f i l t e r e d , washed i n
Found: S=17.05, N=8.74, 1=68.70,
r e q u i r e s , S=17.30, N=7.58, 1=68.61.
4
above 100°C.
( o r CHgClg
The s o l u t i o n was s t i r r e d f o r 48 hours and a b l a c k
p r e c i p i t a t e was o b t a i n e d .
TiI
4
The compound i s i n s o l u b l e i n C C 1
M.P.
4>
decomposition
CHgClg, CSg.
I t changed t o a y e l l o w p r o d u c t when exposed t o a i r .
Zirconium t e t r a c h l o r i d e
ZrCl
4
(0.8 g ) was suspended i n CC1
tetranitride
4
(30 m l ) and t e t r a s u l p h u r
(0.63 g ) added a t room t e m p e r a t u r e .
s o l u t i o n turned r e d .
Immediately t h e
The s o l u t i o n was s t i r r e d f o r 12 hours and a
deep r e d d i s h - o r a n g e p r e c i p i t a t e was o b t a i n e d .
The compound was
-61-
f i l t e r e d , washed i n CC1 and d r i e d i n vacuo.
Found: S=29.55,
4
N=12.80, Cl=33.10, Z r C l . S N
4
M.P. 260°C (decomp.)
4
4
r e q u i r e s : S=30.67, N=13.42, 01=33.99.
I t i s i n s o l u b l e i n CH CI , CS .
The
adduct changed t o a y e l l o w p r o d u c t when exposed t o a i r .
Zirconium t e t r a f l u o r i d e
ZrF
(0.5 g ) was suspended i n d r y methylene d i c h l o r i d e
4
( o r o - d i c h l o r o b e n z e n e ) a t room t e m p e r a t u r e and S N
4
added t o t h e s o l u t i o n .
4
(0.54 g )
The s o l u t i o n was s t i r r e d f o r 48 h o u r s .
No r e a c t i o n was found t o t a k e p l a c e .
Hafnium t e t r a c h l o r i d e
HfCl
4
(1.9 g ) was suspended i n CC1
tetranitride
added a t room t e m p e r a t u r e .
4
(25 m l ) and t e t r a s u l p h u r
The r e a c t i o n m i x t u r e
was s t i r r e d f o r 24 hours and a b r i g h t deep r e d compound was o b t a i n e d .
The p r e c i p i t a t e was f i l t e r e d , washed i n CC1
Found: S=25.41, N=10.35, 01=29.90; S N . H f C l
4
N=11.10, 01=28.14.
4
and d r i e d i n vacuo.
4
4
requires:
M.P. d e c o m p o s i t i o n above 140°C.
i n s o l u b l e i n CH^Clg.
S=25.37,
I t is
The adduct gave a y e l l o w p r o d u c t when
exposed t o a i r .
Antimony p e n t a c h l o r i d e
Antimony p e n t a c h l o r i d e (1.0 m l ) was d i s s o l v e d i n CC1
and a s o l u t i o n o f S N
4
temperature.
4
(0.92 g ) i n CC1
4
(20 m l )
(40 m l ) added a t room
The s o l u t i o n was s t i r r e d f o r 14 h o u r s .
p r e c i p i t a t e was o b t a i n e d .
4
A deep r e d
The p r e c i p i t a t e was f i l t e r e d , washed i n
-62-
CC1
4
and pumped d r y a t room t e m p e r a t u r e . ( O b t a i n e d f o r spectrum o n l y ;
no a n a l y s e s )
Antimony p e n t a f l u o r i d e
SbF (1.9 g ) was suspended i n 25 ml o f CH„C1„ and S J ,
5
2 2
4 4
c
(0.4
g ) added a t room t e m p e r a t u r e .
The s o l u t i o n was s t i r r e d f o r
14 hours and a green p r e c i p i t a t e was o b t a i n e d .
The p r e c i p i t a t e
was f i l t e r e d , washed i n CH^Clg and d r i e d i n vacuo.
N, 5.14; S=11.87; S N .4SbF
4
4
5
Found: F, 38.15,
r e q u i r e s : F, 36.16; N, 5.33; S=12.18.
M.P. 145°C (decomp.)
Niobium p e n t a c h l o r i d e
NbCl
S N
4
4
5
(2.2 g ) was suspended i n CC1
4
(1.4 g ) added a t room t e m p e r a t u r e .
o r CH C1
2
2
(35 m l ) and
The s o l u t i o n was s t i r r e d
f o r 12 hours and a r e d d i s h - b r o w n p r e c i p i t a t e was formed.
p r e c i p i t a t e was f i l t e r e d , washed i n CC1
4
and d r i e d
i n vacuo.
adduct was r e c r y s t a l l i s e d from methylene d i c h l o r i d e .
M.P. 106°C.
The
Found:
S=27.15, N=12.68, Cl=39.50; S ^ . N b C l g r e q u i r e s : S=28.17,
Cl=39.06.
The
N=12.32,
The adduct i s s o l u b l e i n CH CI , CS_.
I t changed t o a y e l l o w p r o d u c t i n a i r .
Niobium p e n t a f l u o r i d e
NbF
and
S N
4
4
o
(1.35 g ) was suspended i n 40 ml o f d r y methylene
(0.2 g ) was added a t room t e m p e r a t u r e .
Immediately a deep
red s o l u t i o n and a p i n k i s h - w h i t e p r e c i p i t a t e was o b t a i n e d .
s o l u t i o n was s t i r r e d
f o r 24 h o u r s .
dichloride
The
The deep r e d s o l u t i o n was
f i l t e r e d and e v a p o r a t e d t o a s m a l l volume (10 m l ) .
A deep red-orange
-63-
p r e c i p i t a t e was f i l t e r e d , washed i n CH C I
dried.
(5 m l ) and vacuum
Found: N= 14.35; S.N. ,NbF_ r e q u i r e s : N =15.04.
4 4
M.P.
5
O
decomp. above 60 C.
i n moist a i r .
The adduct changed t o a y e l l o w p r o d u c t
The i n f r a r e d spectrum o f t h e p i n k i s h - w h i t e
1
p r e c i p i t a t e showed peaks ( a t 3030 and 1612 cm ) due t o -OH
i n d i c a t i n g presence o f p a r t i a l l y h y d r o l y s e d NbF,..
o
Tantalum p e n t a c h l o r i d e
TaCl
and
(2.5 g ) was suspended i n CC1
tetrasulphur tetranitride
o r CH C I , (40 m l )
(1.2 g ) added a t room t e m p e r a t u r e .
Immediately a r e d p r e c i p i t a t e ..was formed.
The s o l u t i o n
was
s t i r r e d f o r 14 hours and a deep r e d compound was o b t a i n e d .
The
compound was f i l t e r e d and d r i e d i n vacuo and r e c r y s t a l l i s e d from
dry methylene d i c h l o r i d e .
S N TaCl
4
4
5
r e q u i r e s : S=23.59, N=10.32, Cl=32.72.
(decomp).
c
M.P.
I t changes t o a y e l l o w p r o d u c t i n a i r .
adduct i s s o l u b l e i n C C 1
TaCl
Found: S=23.40, N=10.88, Cl=33.20;
i n CH C1
0
0
4>
CHgClg, CSg.
132°C
The
The s o l u b i l i t y o f S N
4
4 >
i s Ca. 0. 8g/100 m l .
Tantalum p e n t a f l u o r i d e
TaFg (1.0 g) was suspended i n 70 ml o f d r y CHgClg and
tetrasulphur t e t r a n i t r i d e
(0.15 g ) added a t room t e m p e r a t u r e .
s o l u t i o n was s t i r r e d f o r 48 h o u r s , a deep r e d s o l u t i o n and a
w h i t e p r e c i p i t a t e was o b t a i n e d .
The s o l u t i o n was f i l t e r e d ,
the f i l t r a t e was evaporated t o a s m a l l volume ( 1 0 m l ) and a deep
The
-64-
b r i g h t r e d p r e c i p i t a t e was o b t a i n e d .
The p r e c i p i t a t e was
f i l t e r e d and washed i n CHgCl^ (5 m l ) and pumped d r y a t room
temperature.
Found: S=26.59, N=12.24; S N . T a F
4
S=27.81, N=12.17.
4
5
requires:
The compound changed t o a y e l l o w p r o d u c t
when exposed t o a i r .
Tungsten h e x a c h l o r i d e
WCl. (2.0 g ) was suspended i n CC1. (40 m l ) and S.N. (0.72 g )
b
4
4 4
added a t room t e m p e r a t u r e .
was formed.
Immediately a dark-brown p r e c i p i t a t e
The s o l u t i o n was s t i r r e d f o r 24 h o u r s .
p r e c i p i t a t e was f i l t e r e d , washed i n CC1
temperature.
4
The
and pumped d r y a t room
( O b t a i n e d f o r spectum o n l y ; no a n a l y s e s ) .
Tungsten hexabromide
WBr_ (1.2 g ) was d i s s o l v e d i n carbon d i s u l p h i d e a t room
£>
temperatur e and S.N
(0.4 g ) added t o t h e s o l u t i o n .
a dark-brown p r e c i p i t a t e was formed.
f o r 48 h o u r s .
i n CS
Immediately
The s o l u t i o n was s t i r r e d
The dark-brown p r e c i p i t a t e was f i l t e r e d ,
and d r i e d
N=8.08, Br=44.5.
i n vacuo a t room t e m p e r a t u r e .
washed
Found: S=17.85,
S ^ . W B ^ r e q u i r e s , S, 18.61, N=8.14, B r , 46.48.
M.P. 251°C.
Tungsten o x y t e t r a c h l o r i d e
W0C1
4
(0.2 g ) was d i s s o l v e d i n d r y benzene (20 m l ) and S N
4
( 0 . 1 g ) added a t room t e m p e r a t u r e .
immediately formed.
4
A dark-brown p r e c i p i t a t e was
The s o l u t i o n was s t i r r e d f o r 10 h o u r s .
The p r e c i p i t a t e was f i l t e r e d , washed i n benzene and pumped d r y .
-65-
Since t h e i n f r a r e d spectrum o f t h e compound was s i m i l a r t o t h a t
o f WBr .S N , t h i s compound i s p r o b a b l y W0C1 .S N .
4
4
4
4
4
4
There
(H
was i n s u f f i c i e n t compound f o r analyses and o t h e r i n v e s t i g a t i o n s .
Vanadium o x y t r i c h l o r i d e
1 ml o f VOClg was d i s s o l v e d i n 20 ml o f d r y e t h e r and
S
N
4 4
S) added a t room t e m p e r a t u r e .
brown p r e c i p i t a t e was formed.
. Immediately a dark
The s o l u t i o n was s t i r r e d f o r 14
hours and t h e p r e c i p i t a t e was f i l t e r e d , washed i n e t h e r and
d r i e d i n vacuo.
Since
t h e i n f r a r e d spectrum o f t h e p r o d u c t
showed some h y d r o l y s i s o f t h e compound, t h e compound was n o t
investigated
further.
Vanadium t r i c h l o r i d e
VC1
3
(1.0 g ) and t e t r a s u l p h u r t e t r a n i t r i d e i n 40 ml
o f d r y e t h e r were shaken t o g e t h e r f o r s e v e r a l h o u r s . a t room
temperature.
Aluminium
No r e a c t i o n was
observed.
tribromide
The r e a c t i o n was s t u d i e d i n C C 1
t o l u e n e , CSg and CHBrg.
4>
Carbon d i s u l p h i d e and bromoform were found t o be s u i t a b l e s o l v e n t s .
(i) AlBr
3
(1.2 g ) was d i s s o l v e d i n CC1
4
o r t o l u e n e (25 m l ) and
t e t r a s u l p h u r t e t r a n i t r i d e (0.4 g ) added a t room t e m p e r a t u r e ,
a
Immediately d a r k - r e d s o l u t i o n was o b t a i n e d .
The s o l u t i o n was
s t i r r e d f o r 14 hours and a b l a c k s t i c k y mass was o b t a i n e d .
r e a c t i o n was n o t s t u d i e d f u r t h e r .
The
-66-
( i i ) A l B r ^ ( 1 . 5 g ) was d i s s o l v e d i n c a r b o n d i s u l p h i d e o r bromoform
(20 m l ) and t e t r a s u l p h u r t e t r a n i t r i d e ( 0 . 5 1 g ) added a t room
temperature.
I m m e d i a t e l y a r e d s o l u t i o n was o b t a i n e d .
The
s o l u t i o n was s t i r r e d f o r 24 h o u r s and a n orange-brown compound
was o b t a i n e d .
The compound was f i l t e r e d , washed i n CSg and vacuum
d r i e d a t room t e m p e r a t u r e .
Found: S=16.04, N=6.97, B r = 6 8 . 7 4
S N . 2 A l B r r e q u i r e s ; S=17.83, N=7.80, Br=66.81.
M.P. 144°C.
The compound i s s l i g h t l y s o l u b l e i n CS^.
I t changed t o a y e l l o w
p r o d u c t upon e x p o s u r e t o a i r .
Aluminium t r i c h l o r i d e
J
4
4
3
A1C1
o
( 1 . 9 g ) was
dissolved
( o r C C 1 > and t e t r a s u l p h u r
4
temperature.
s o l u t i o n was
i n 35 ml o f c a r b o n
tetranitride
A deep r e d s o l u t i o n was
disulphide
( 1 . 3 g ) added a t room
formed i m m e d i a t e l y .
The
s t i r r e d f o r 14 h o u r s and a deep r e d p r e c i p i t a t e
obtained.
The compound was
i n vacuo.
The a d d u c t was
f i l t e r e d , washed i n CS
r e c r y s t a l l i s e d from CHgClg.
S, 29.45, N ^ 1 2 ^ 4 ] ^ S N . 2 A 1 C 1
4
Cl=48.60rci=47.25.
4
M.P.
and
3
was
dried
Found:
r e q u i r e s : S=28.38, N=12.41,
89°C (decomp.)
I t changed
to a yellow
product i n a i r .
Gallium
trichloride
( i ) GaClg
( 1 . 0 5 g ) was
and t e t r a s u l p h u r
A sticky
dissolved
tetranitride
4
or pentane
(20 ml)
( 0 . 5 5 g ) added a t room t e m p e r a t u r e .
d a r k - r e d p r e c i p i t a t e was
s o l u t i o n was
i n CC1
immediately obtained.
s t i r r e d f o r 10 h o u r s and
filtered.
The
The
product
-67-
was
pumped d r y .
The r e a c t i o n was
o i l y p r o d u c t was
( i i ) GaCl
difficult
( 1 . 0 g ) was
not s t u d i e d
further since
the
to handle.
dissolved
i n carbon d i s u l p h i d e (15 ml)
3
and t e t r a s u l p h u r
t e t r a n i t r i d e ( 0 . 5 g ) added a t room t e m p e r a t u r e .
I m m e d i a t e l y a deep r e d p r e c i p i t a t e was
was
stirred
f o r 24 h o u r s .
washed i n CS
and
The
vacuum d r i e d a t room t e m p e r a t u r e .
4
N=10.44, C l = 3 9 . 7 1 .
I t changes
solution
The deep r e d p r e c i p i t a t e was
S=23.48, N=11.22, 01=37.89, S N . 2 G a C l
CSg.
obtained.
4
3
filtered,
Found:
r e q u i r e s , S=23.87,
M.P. 100°C (decomp.)
I t i s soluble i n
t o a y e l l o w compound i n a i r .
Indium t r i c h l o r i d e
InClg
( 0 . 8 g ) was
suspended
(20 m l ) and t e t r a s u l p h u r
temperature.
was
stirred
slowly
No
formed.
and d r i e d
r e a c t i o n was
The compound was
,2InCl
observed.
A deep r e d d i s h - b r o w n
f i l t e r e d , wa
i n vacuo a t room t e m p e r a t u r e .
01=34.99; S N
dichloride
t e t r a n i t r i d e ( 0 . 3 3 g ) added a t room
immediate
f o r 48 h o u r s .
i n methylene
The
solution
precipitate
was
s h e d i n CHgClg
Found: S=20.30, N=9.33,
r e q u i r e s ; S=20.42, N=8.94, 01=33.99.
M.P.
o
decomp. above 100 C.
exposed
to a i r .
I t changed
I t i s slightly
t o a y e l l o w p r o d u c t when
soluble
i n methylene
dichloride.
Thallium t r i c h l o r i d e
T1C1^.(0.4 g ) was
chlorine
suspended
i n dry a c e t o n i t r i l e (25 ml)
and
gas ( d r i e d o v e r P_0 ) was p a s s e d t h r o u g h t h e s o l u t i o n
till
-68-
all
t h e t h a l l o u s c h l o r i d e was
was
obtained.
dissolved
E x c e s s o f c h l o r i n e was
and a c l e a r
removed by
solution
flushing
o
out w i t h dry n i t r o g e n and by c o n d e n s i n g i t a t -196
T e t r a s u l p h u r t e t r a n i t r i d e ( 0 . 1 5 g ) was
s o l u t i o n a t room t e m p e r a t u r e .
o r a n g e - y e l l o w s o l u t i o n was
t h e n added t o t h e above
After
about
obtained.
The
10-15 m i n u t e s
s o l u t i o n was
f o r 14 h o u r s and a p a l e y e l l o w s o l u t i o n was
a c e t o n i t r i l e was
of t h e compound was
obtained.
The
S i n c e the i n f r a r e d
s i m i l a r to the I.R. s p e c t r a
S.N..2GaCl,. t h i s compound may
4 4
*$
soluble
formed.
i n CHgClg.
and
spectrum
of S^N^.2InClg,
w e l l be S N .2T1C1 .
4 4
o
T h e r e was
an
stirred
removed by pumping a t room t e m p e r a t u r e
a r e d o i l y compound was
was
C.
The compound
not enough m a t e r i a l
for further
investigations.
Iron ( I I I )
FeCl
3
( 2 . 2 g ) was
tetrasulphur
T h e r e was
48 h o u r s .
was
chloride
suspended
4
and
t e t r a n i t r i d e ( 1 . 2 g ) added a t room t e m p e r a t u r e .
no immediate
reaction.
A brown-black
The s o l u t i o n was
p r e c i p i t a t e was
obtained.
stirred
The
for
precipitate
f i l t e r e d , washed i n C C l ^ and pumped d r y a t room t e m p e r a t u r e .
The compound i s s o l u b l e
CH_C1
0
i n CSg and CH^Cl^
and a deep red-brown a d d u c t was
N,10.5; C I , 4 3 . 7 2 ; S N . 2 F e C l
4
M.P.
i n 40 ml o f d r y C C 1
80°C (decomp.)
4
3
requires:
I t changes
and r e c r y s t a l l i s e d
obtained.
from
Found: 8,24.31,
S=25.16, N=11.01, 01=41.87.
to a y e l l o w product i n a i r .
-69-
R e a c t i o n between t e t r a s u l p h u r
t e t r a n i t r i d e and p h e n y l b o r o n
T e t r a s u l p h u r t e t r a n i t r i d e ( 0 . 4 g ) was
CCl^
( 2 0 m l ) and p h e n y l b o r o n
temperature.
obtained.
dichloride
dissolved
o r a n g e p r e c i p i t a t e was
( 0 . 3 m l ) added a t room
stirred
obtained.
brownish-
The p r e c i p i t a t e was
filtered,
N=15.75, C=19.92, 01=21.30, H=1.33; S ^ . P h B C l
N=16.32, C=20.98, H=1.46, 01=20.69.
compound changed
was
f o r 6 h o u r s and a
washed i n C C l ^ and pumped dry a t room t e m p e r a t u r e .
i.r.
i n dry
I m m e d i a t e l y an o r a n g e - r e d p r e c i p i t a t e
The s o l u t i o n was
dichloride
Found: S=35.10,
requires,
M.P. 99-102°C.
t o a y e l l o w p r o d u c t when e x p o s e d
s p e c t r u m o f t h e p r o d u c t exposed
The
to a i r .
t o a i r f o r 48 h o u r s
t h e p r e s e n c e o f S^N^ and p r o b a b l y p h e n y l b o r o n
S=37.30,
dichloride
The
indicated
hydrolysis
products.
R e a c t i o n between t e t r a s u l p h u r
0.7
CCl^
ml
t e t r a n i t r i d e and p - t o l y t i n t r i c h l o r i d e
( 1 . 2 g ) o f p - t o l y t i n t r i c h l o r i d e was
( 3 0 m l ) and t e t r a s u l p h u r
temperature.
No
s o l u t i o n was
stirred
slowly
formed and
and d r i e d
immediate
colour
filtered.
The
4
4
observed.
A deep r e d p r e c i p i t a t e
The
was
washed i n C C l ^
i n f r a r e d s p e c t r u m o f t h e compound was
n
4
change was
The p r e c i p i t a t e was
to t h e i n f r a r e d s p e c t r u m o f S C l
01=12.75, S n C l . 2 S N
i n dry
t e t r a n i t r i d e ( 0 . 4 g ) added a t room
f o r 60 h o u r s .
i n vacuo.
dissolved
requires;
4 <
2S N .
4
4
identical
Found: S=38.60, N=17.90,
S=40.73, N=17.80, 01=22.57.
The
ation
p - T o l y t i n t r i c h l o r i d e had undergone d i s p r o p o r t i o n
of S N
A
giving SnCl
.2S.N
and
tetra-p-tolyltin.
i n the presence
-70-
R e a c t i o n between t r i m e t h y l a l u m i n i u m
The r e a c t i o n was
tetranitride
0.75
suspended
c o o l e d t o -196°C.
r e c o v e r e d by
Tetrasulphur
and
T r i m e t h y l aluminium
( 1 ml,
The s o l u t i o n was
slowly
warmed t o room t e m p e r a t u r e and s t i r r e d
v i s i b l e change o c c u r r e d and
tetranitride
i n 25 ml o f d r y C C l ^
g ) added t o t h e above s o l u t i o n .
of S^N^ was
tetrasulphur
c a r r i e d out i n d r y h e x a n e .
( 1 . 9 g ) was
the s o l u t i o n was
and
f o r 24 h o u r s .
No
the unreacted y e l l o w p r e c i p i t a t e
filtration.
R e a c t i o n between p h e n y l m e r c u r i c c h l o r i d e and
tetranitride
Phenylmercuric chloride
tetrasulphur
( 1 . 0 g ) and S^N^ ( 0 . 5 8 g ) were
s h a k e n t o g e t h e r i n 40 ml o f dry e t h e r f o r 14 hours..
No
reaction
R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e and s u l p h u r y 1
chloride
was
observed.
Tetrasulphur tetranitride
of dry t o l u e n e a t -196°C.
under
( 0 . 4 9 g ) was
suspended
Sulphury1 c h l o r i d e
a c u r r e n t of dry n i t r o g e n gas.
The
( 1 . 0 m l ) added
r e a c t i o n mixture
was
s l o w l y warmed t o room t e m p e r a t u r e , b u t no o b v i o u s
was
observed.
The s o l u t i o n was
stirred
i n 30 ml
reaction
f o r 16 h o u r s , t h e
i n f r a r e d s p e c t r u m o f t h e e v a p o r a t e d p r o d u c t showed t h e unchanged
starting
material.
I n another experiment
t h e r e a c t i o n was
a b s e n c e o f t h e s o l v e n t a t room t e m p e r a t u r e
trithiazyl
t r i c h l o r i d e was
obtained.
c a r r i e d out i n t h e
( s e e page 4 8 ) , and
Found: S = 3 9 . 4 ; N=17.60;
-71-
C l = 43.40; mol.wt ( c r y o s c o p i c i n b e n z e n e )
244; S N C I
requires
o o o
S=39.31; N=17.16; 01=43.45; mol.wt. = 244.57.
g i v e s NSC1
slightly
S0
2
S_N„ .probably
on pumping, s i n c e t h e S N C I
i n the f l a s k turned
Jo. o
g r e e n under
vacuum.
i n moist a i r ( 2 S N C 1
3
3
I t forms ammonium c h l o r i d e
+ 12H 0 -5
3
2
6NH C1 + 6 S 0 )
4
2
R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e and
( a ) 1.5
was
chlorine
g o f f i n e l y powdered t e t r a s u l p h u r t e t r a n i t r i d e
suspended
and
was
i n d r y C C l ^ ( 2 0 m l ) and c h l o r i n e gas ( d r i e d o v e r
P
2^5^
c a r e f u l l y p a s s e d t h r o u g h t h e s o l u t i o n a t room t e m p e r a t u r e f o r
about
5 minutes
s o l u t i o n was
u n t i l a l l t h e S.N. was
4 4
obtained.
d i s s o l v e d and a c l e a r r e d
E x c e s s o f c h l o r i n e g a s was
removed by
out w i t h d r y n i t r o g e n gas and c o n d e n s i n g i t a t -196°C.
s o l u t i o n was
c o o l e d t o -16°C
c r y s t a l s were o b t a i n e d .
a t room t e m p e r a t u r e .
M.P.
The p r e c i p i t a t e was
The compound was
89-91°C.
The r e d
u s i n g c o l d r e f r i g e r a t o r and b r i g h t r e d
Found: S=37.54, N=17.82, C l = 4 3 . 3 0 ;
Cl=43.45.
f i l t e r e d and pumped d r y
reerystallised
from d r y
The compound t u r n s w h i t e i n m o i s t a i r ( c f .
(see (b) below).
and more SgNgClg was
CCl^.
SgNgClg r e q u i r e s , S=39.36, N=17.16,
S^N^/SOgClg p r o d u c t but c o n t r a s t p r o d u c t o b t a i n e d w i t h a f a s t
of c h l o r i n e
flushing
The
f i l t r a t e was
flow
evaporated to dryness
obtained.
(b) Tetrasulphur t e t r a n i t r i d e
( 1 . 5 g ) was
suspended
a t room t e m p e r a t u r e and d r y c h l o r i n e gas was
i n C C l ^ (20 ml)
passed a t a very
fast
-72-
r a t e through the s o l u t i o n .
First
a f t e r 2-3 m i n u t e s a r e d s o l u t i o n
was o b t a i n e d , t h e b u b b l i n g o f c h l o r i n e gas was c o n t i n u e d and a
y e l l o w p r e c i p i t a t e came out o f t h e s o l u t i o n a f t e r
10 m i n u t e s .
The f l o w o f c h l o r i n e gas was s t o p p e d a f t e r 4 j h o u r s .
The y e l l o w
p r e c i p i t a t e was f i l t e r e d and vacuum d r i e d a t room t e m p e r a t u r e .
compound was r e c r y s t a l l i s e d
from d r y C C l ^ .
Found:
The
(before
r e c r y s t a l l i s a t i o n ) , S=36.80, N=21.90, 01=27.60 ( 2 n d . 2 9 . 4 6 ) ;
( r e c r y s t a l l i s e d compound), S=45.70, N=23.60, 01=26.90. M.P.58-64°C(decomp.)
( r e p e a t p r e p a r a t i o n ) , S=43.79, N=19.59, 01=36.90.
SgNgClg
requires:
S=50.19, N=21.90, 01=27.84; S g N g C ^ r e q u i r e s : S=45.93, N=20.10, 01=33.91.
The compound changed t o a y e l l o w - b l a c k compound i n m o i s t a i r .
I . R . s p e c t r u m o f t h e b l a c k y e l l o w compound exposed
e x h i b i t e d p e a k s m a i n l y due t o S^N^ and -OH.
S_N_C1. showed t h e f o l l o w i n g p e a k s :
bo
4
t o a i r f o r 48 h o u r s
The i n f r a r e d s p e c t r u m o f
1011 v s , 948 m s ( s h ) , 899 ( s h ) ,
780 ms, 699 s ( s h ) , 686 v s , 670 v w ( s h ) , 862 v s , 627 v w ( s h ) , 577 s ,
546 v s , 517 w ( s h ) , 504 ms,
(452 s ) .
( c ) T e t r a s u l p h u r t e t r a n i t r i d e was d i s s o l v e d
and d r y c h l o r i n e gas was b u b b l e d
through t h e s o l u t i o n a t a very slow
r a t e a t room t e m p e r a t u r e f o r about
obtained.
3 h o u r s and a r e d s o l u t i o n
was
The s o l u t i o n was e v a p o r a t e d t o a s m a l l volume ( 2 0 m l )
by pumping and c o o l e d t o -16°C.
was o b t a i n e d .
82-85°C.
i n dry C C l ^ (50 ml)
A b r i g h t y e l l o w c r y s t a l l i n e compound
Found: 01=42.90, SgNgClg r e q u i r e s ; 01=43.45.
M.P.
-73R e a c t i o n between t e t r a s u l p h u r t e t r a n i t r i d e and bromine
The r e a c t i o n was c a r r i e d o u t i n a n a t m o s p h e r e o f d r y
n i t r o g e n g a s i n a 50 ml two-necked round-bottomed
flask.
Bromine ( 2 0 m l ) d r i e d o v e r p h o s p h o r u s p e n t o x i d e was c o n d e n s e d
on t e t r a s u l p h u r t e t r a n i t r i d e
( 1 . 0 g ) a t -196°C and t h e
r e a c t i o n f l a s k was warmed t o room t e m p e r a t u r e .
Carbon d i s u l p h i d e
( 2 0 m l ) was t h e n added t o t h e above s o l u t i o n and t h e l i q u i d
stirred
f o r 14 h o u r s a t room t e m p e r a t u r e ,
p r e c i p i t a t e was s l o w l y formed.
was
A deep r e d d i s h - b r o w n
The e x c e s s o f s o l v e n t and
bromine was removed by pumping a t room t e m p e r a t u r e and a deep r e d brown p r e c i p i t a t e was o b t a i n e d .
Br=66.10; ( N S B r )
n
Found: S=26.40, N=11.50,
r e q u i r e s : S=25.41, N=11.19, B r = 6 3 . 4 5 .
The compound was i n s o l u b l e i n C S g .
0
M.P. 1 2 1 C „
675 v s , 609 w,
I t i s moisture
Mol.Wt.
sensitive.
I n f r a r e d a b s o r p t i o n s o c c u r a t : 1169 v s , 1010 v s ,
574 vw
(sh),
562 s , 537 w,
492 v s .
R e a c t i o n between S^ii^Cl^ and bromine
Dry bromine 15 ml was c o n d e n s e d i n 1.0 g o f S ^ N ^ C l ^ i n
a two-necked round-bottomed f l a s k and t h e s o l u t i o n was s t i r r e d f o r
6 h o u r s a t room t e m p e r a t u r e .
E x c e s s of bromine was removed
pumping and a y e l l o w compound was o b t a i n e d .
found t o c o n t a i n c h l o r i n e and b r o m i n e .
investigated
further.
1018 s , 959vw, 763 vw,
by
The compound was
The r e a c t i o n was n o t
I n f r a r e d a b s o r p t i o n s o c c u r a t : 1100 s ,
724 w,
621 vw, 534 v s , 515 v v w ( s h ) .
-74-
R e a c t i o n s of t r i t h i a z y l t r i c h l o r i d e
In a l l the r e a c t i o n s s t u d i e d ,
and
SOgClg was
4
used a s t h e s t a r t i n g m a t e r i a l .
R e a c t i o n between t r i t h i a z y l
S N CI
SgNgClg p r e p a r e d from S ^ N
(0.7
g) was
dissolved
t e m p e r a t u r e and
dry
solution.
s o l u t i o n was
The
p r e c i p i t a t e was
t r i c h l o r i d e and
c h l o r i n e gas
i n CC1
chlorine
(25 ml)
a t room
passed f o r 2 hours through
c o o l e d t o -16°C
obtained, f i l t e r e d
and
and
dried
a yellow-white
i n vacuo.
The
i n f r a r e d s p e c t r u m o f t h e compound showed t h a t S N C I
had
o o o
no c h a n g e .
Attempted p r e p a r a t i o n
of S N
the
undergone
CI
O o
S_N C I
(0.89
g) was
dissolved
d i c h l o r i d e a t room t e m p e r a t u r e and
added t o t h e s o l u t i o n .
s o l u t i o n was
stirred
p r e c i p i t a t e was
i n vacuo.
The
(No
i n 20 ml
tetrasulphur
The
methylene
t e t r a n i t r i d e (1.0
immediate r e a c t i o n was
f o r 12 h o u r s and
obtained.
o f dry
observed).
o
c o o l e d t o -16
p r e c i p i t a t e was
C.
A
filtered
I . R . s p e c t r u m showed t h a t t h e compound was
d r y n e s s and
f i l t r a t e was
a m i x t u r e o f S N ^ and
4
The
yellow
and
dried
S^N^.
e v a p o r a t e d t o / t h e i n f r a r e d s p e c t r u m of t h e
p r o d u c t i n d i c a t i n g t h a t i t was
g)
yellow
trithiazyl
trichloride.
Attempted o x i d a t i o n
of t r i t h i a z y l t r i c h l o r i d e
A t t e m p t s were made t o p r e p a r e s u l p h a n u r i c
by t h e
iodine
chloride
(S^N^O^d^)
o x i d a t i o n of t r i t h i a z y l t r i c h l o r i d e u s i n g s e l e n i u m
p e n t o x i d e and ozone a s t h e o x i d i s i n g a g e n t s .
dioxide,
-75-
( a ) Attempted o x i d a t i o n
of s K C I
Trithiazyl trichloride
(30 ml)
The
and
selenium dioxide
s o l u t i o n was
stirred
a pinkish-white
f i l t e r e d and
obtained.
g ) was
(0.79
f o r 1-2
r e a c t i o n , t h e . s o l u t i o n was
and
(1.0
using
p r e c i p i t a t e was
evaporated to d r y n e s s .
I.ft. spectra
the crude red product i n d i c a t e d
was
formed.
r e a c t i o n was
(b) Attempted o x i d a t i o n
S_N C I
iodine
(0.5
not
Since
dissolved
obtained.
t h a t no
solution
studied
of dry
s o l u t i o n was
and
a b r o w n - c o l o u r e d s o l u t i o n were o b t a i n e d .
obtained.
The
CC1.
i . r . spectrum of
further.
r e a c t i o n was
f o r 24 h o u r s and
and
The
seen to take
solution
place.
a pink-white p r e c i p i t a t e
The
solution
a brown p r e c i p i t a t e
was
was
i . r . s p e c t r u m o f t h e p i n k - w h i t e p r e c i p i t a t e showed
t h a t t h e compound was
sulphanuric
chloride
l2°5
i n 25 ml
e v a p o r a t e d t o d r y n e s s and
was
further.
The
f i l t e r e d and
was
p r e c i p i t a t e (SeOg)
sulphanuric
stirred
the
The
obvious
solution
A crude red product
was
refluxed
no
no
A red
p e n t o x i d e ( 0 . 5 g ) added a t room t e m p e r a t u r e .
f o r 1 h o u r but
CCl^
t h e r e was
for 6 hours.
of S^N^Cl^ u s i n g
g ) was
i n dry
g) added a t room t e m p e r a t u r e .
of t h e p i n k i s h - w h i t e
and
The
dissolved
hours.
refluxed
SeO
a m i x t u r e of
IgOg and
s i l i c o n e grease, whereas
t h e brown p r e c i p i t a t e i n d i c a t e d
c h l o r i d e was
formed.
The
p r o d u c t was
that
not
no
investigated
-76-
( c ) Attempted
o x i d a t i o n o f S ^ N ^ C l ^ u s i n g Ozone
(i) Trithiazyl
trichloride
( 2 . 0 g ) was
CC1. ( 5 0 m l ) and ozone-oxygen m i x t u r e
dissolved
i n dry
( d r i e d o v e r P „ 0 ) was
O
bubbled
t h r o u g h t h e s o l u t i o n a t v e r y s l o w r a t e a t -10
The
f l o w o f ozone was
was
e v a p o r a t e d t o d r y n e s s and a w h i t e - y e l l o w p r e c i p i t a t e
obtained.
d i s c o n t i n u e d a f t e r 48 h o u r s .
C.
I . R . s p e c t r u m o f t h e compound showed t h a t
had undergone no
trichloride
( 2 . 0 g ) was
was
S^N^Cl^
dissolved i n
50 ml o f d r y C C l ^ and ozone-oxygen m i x t u r e was
o
passed
t h e s o l u t i o n a t 60 C a t s l o w r a t e f o r 24 h o u r s .
of product
( i i i ) The
solution
change.
(iO T r i t h i a z y l
spectrum
The
showed t h a t S N C I
o x i d a t i o n was
The
i.r.
had undergone no
also carried
change.
out i n t h e p r e s e n c e
o f Mo0_ a s a c a t a l y s t a s a b o v e , b u t no S„N 0 C I
O
through
o O o
formation
was
o
noticed.
R e a c t i o n between t r i t h i a z y l
Trithiazyl
trichloride
t r i c h l o r i d e and
( 0 . 9 0 g ) was
t a k e n i n a 100 ml
n e c k e d , round-bottomed f l a s k and p y r i d i n e
The
f l a s k was
t o a p a l e y e l l o w and
finally
Dry p e n t a n e
s o l u t i o n was
stirred
a red oily
( 2 5 m l ) was
two-
( o . 9 m l ) added a t
s l o w l y warmed t o room t e m p e r a t u r e .
o f t h e s o l u t i o n t u r n e d g r e e n a f t e r about
obtained.
pyridine
0°C.
The c o l o u r
10 m i n u t e s , t h e n changed
t h i c k p a s t y mass
was
added t o t h e o i l y mass and
f o r 12-J-14 h o u r s a t room t e m p e r a t u r e .
A
the
-77-
y e l l o w - b r o w n p r e c i p i t a t e was o b t a i n e d , f i l t e r e d , washed i n
p e n t a n e and d r i e d
i n vacuo.
Found: C=31.05, H=3.66, N=15.00,
S=17.20, C l = 2 9 . 0 , S N C l . 2 p y r e q u i r e s ;
3
3
3
N=17.39, S=23.85, C l = 2 6 . 4 6 ,
C=29.81, H=2.46,
(SgNgClg.Spy r e q u i r e s ; C=37.38,
H=3.12, N=17.45, S=19.94, C l = 2 2 . 1 2 .
R e a c t i o n p r o b a b l y needs
to be r e p e a t e d a n d s t o p p e d a t p a l e y e l l o w s t a g e .
Infrared
s p e c t r u m showed p e a k s a t : 1259 vw, 1226 vw, 1180 w, 1122 vvw ( s h
1104 w, 1068 ms, 1047 w ( s h ) , 1022 ms, 1000 w, 961 vvw, ( 9 2 6 w)
841 v s , 779 v s , 758 v s , 743 v v w ( s h ) , 722 v w ( s h ) , 701 vvw, 679 v s
666 vvw ( s h ) , 660 v w ( s h ) , 621 v s , 608 vw, 600 w, 560 v s , 542 s ,
491 w, 454 vw.
R e a c t i o n between
Trithiazyl
d i p h e n y l mercury and t r i t h i a z y l t r i c h l o r i d e
t r i c h l o r i d e ( 1 . 2 g ) was d i s s o l v e d
ml o l d r y benzene and d i p h e n y l mercury
temperature.
out
i n about 25
( 1 . 7 g ) added a t room
I m m e d i a t e l y a y e l l o w - g r e e n p r e c i p i t a t e came
of the s o l u t i o n ,
the solution
t u r n e d green a f t e r about 5
m i n u t e s and a f t e r 3 h o u r s a b l a c k p r e c i p i t a t e was o b t a i n e d .
The s o l u t i o n was s t i r r e d
was
f o r 12 h o u r s .
The b l a c k
precipitate
f i l t e r e d and t h e f i l t r a t e e v a p o r a t e d t o d r y n e s s , no p p t
was o b t a i n e d .
The b l a c k p r e c i p i t a t e was washed
pumped d r y a t room t e m p e r a t u r e .
C=23.61, H=1.57; SgN C I
Found:^16.50, N=8.06, C l = 1 8 . 6 0 ,
.(PlOgHg r e q u i r e s ;
C l = 1 7 . 7 7 , C l = 2 4 . 0 3 , H=1.67.
i n benzene and
M.P.
170°C.
S=16.02, N=7.01,
I t i s insoluble
-78-
i n methylene d i c h l o r i d e .
I n f r a r e d absorptions occur a t :
2198 ms, 1156 vw, 1064 v w ( s h ) , 1047 v s , 1020 vvw, 990 v s ,
916 vvw, 855 ms, 797 vvw, 646 v s , 722 v s , 685 v s , 660 m s ( s h ) ,
609 w, 571 ms, 531 v s , 508 v s , 465 w, 436 w, 431 v s , 408 m s ( s h ) ,
-1
394 v s , 347 v s , 330 vw,
(309 w,
R e a c t i o n between t r i t h i a z y l
SbCl
279 s ) , ( 2 2 7 w,
i n thionyl
chloride
The
t h e f i l t r a t e was e v a p o r a t e d t o
d r y n e s s and a c r u d e d a r k o i l p r o d u c t was o b t a i n e d .
brown p r e c i p i t a t e was washed i n S0C1
1
solution
f o r 12 h o u r s and a dark-brown p r e c i p i t a t e was o b t a i n e d .
The p r e c i p i t a t e was f i l t e r e d ,
I
I
(20 ml)
t r i c h l o r i d e ( 2 . 0 g ) added a t room t e m p e r a t u r e .
I m m e d i a t e l y a dark-brown s o l u t i o n was o b t a i n e d .
was s t i r r e d
.
t r i c h l o r i d e and antimony t r i c h l o r i d e i n S0C1
( 0 . 7 g ) was d i s s o l v e d
and t r i t h i a z y l
211 w) cm
The d a r k -
and a y e l l o w - p a l e g r e e n
p r e c i p i t a t e was o b t a i n e d .
Found: S=23.10, N=6.76, 01=48.70;
S.N SbCl
r e q u i r e s : S=22.25, N=7.3, 01=49.30.
Infrared r
4 3
9
0
a b s o r p t i o n s o c c u r a t : 217 ms,
1010 v s , 803 ms,
418 w. cm
1
126 vw,
1193 w,
1149 vw,
735 v v w ( s h ) , 719 ms, 666 vvw, 626 ms,
( 4 5 0 ms)
.
R e a c t i o n between t r i t h i a z y l
in thionyl chloride.
t r i c h l o r i d e and t i t a n i u m
T r i t h i a z y l t r i c h l o r i d e ( 0 . 5 g ) was d i s s o l v e d
chloride
1057 s ,
( 1 0 m l ) and t i t a n i u m t e t r a c h l o r i d e
tetrachloride
i n thionyl-
( 1 m l ) added a t room
a
temperature.
I m m e d i a t e l y / d e e p r e d s o l u t i o n was o b t a i n e d .
s o l u t i o n was s t i r r e d
f o r 4 h o u r s and a deep r e d p r e c i p i t a t e
The
was
-79-
obtained.
The p r e c i p i t a t e was
f i l t e r e d , washed i n S 0 C l
and
o
•tf:
pumped dry a t room t e m p e r a t u r e .
T i
S
N
2 2 3
C 1
6
r e (
l
u i r e s
»
Found: S=16.0, N=9.60,^ C l = 5 2 . 0 0 ,
S=15.43, N=10.31, 01=51.36,
I n f r a r e d s p e c t r u m showed t h e f o l l o w i n g p e a k s :
M.P.
70°C (decomp.)
1324 w, 1012 v s ,
966 v s , 840 v s , 732 v s , 697 s , 662 s , 608 v s , ( 5 0 0 0 v s ) cm
R e a c t i o n between t r i t h i a z y l
i n thtonyl c h l o r i d e
SJ
CI
( 0 . 2 g ) was
trichloride
1
.
and antimony p e n t a c h l o r i d e
d i s s o l v e d i n 10 ml o f S0C1
and
SbCl
a
( 1 m l ) added a t room t e m p e r a t u r e .
s o l u t i o n was
obtained.
The s o l u t i o n was
and e x c e s s o f t h e l i q u i d was
The
s t i r r e d f o r 2-3
i n f r a r e d s p e c t r u m o f t h e compound was
further investigations.
1156 vw,
619 w,
1117 ms, 1058
599
s , 555 w,
hours
comparable
T h e r e was
to the
insufficient
compound
I.R. absorptions occur a t :
v s , 1017
v s , 866 ms, 722 ms, 687 s , 666
513 v s ( 4 5 4 s ) , 431 ms cm
R e a c t i o n between t r i t h i a z y l
orange
removed by pumping a t room t e m p e r a t u r e .
i n f r a r e d spectrum of T i S N C I .
Z 2, o b
for
Immediately/bright
1
w,
.
trichloride
and
epoxides
( 2 . 0 g ) was
takem i n a S c h l e n k
( i ) Epichlorohydrin
Trithiazyl trichloride
epichlorohydrin
dry
(15-16 m l ) added a t -196°C under
nitrogen gas.
m i x t u r e was
V i g o r o u s r e a c t i o n was
after
o b s e r v e d and
s l o w l y warmed t o room t e m p e r a t u r e .
a g r e e n s o l u t i o n was
1-2 h o u r s .
a current
o b t a i n e d w h i c h changed
F i n a l l y a r e d l i q u i d was
After
the
and
of
reaction
15-20
minutes
to a p a l e - y e l l o w l i q u i d
obtained a f t e r
12-14
hours,
-80-
and t h e r e was no f u r t h e r c o l o u r c h a n g e .
E x c e s s of e p i c h l o r o h y d r i n
was removed by pumping a t room t e m p e r a t u r e and a r e d o i l
obtained.
The r e d o i l changed t o s t i c k y mass a f t e r 2-3
d r y h e x a n e ( 1 0 m l ) was added t o i t ,
f o r 12-14 h o u r s .
and t h e s o l u t i o n was
was
days,
stirred
A r e d d i s h - b r o w n s o l i d was formed, t h e s o l i d
was washed i n e t h a n o l and f i n e powdery w h i t e compound was
Found: S=18.68, N=8.3, C=20.70,
CH .C1)
2
3
obtained.
H=2.78, 01=40.60, S ^ r O - C H g - C H - C l .
r e q u i r e s : S,18.65; N=8.26; C,20.3; H,2.87; C I , 4 0 . 9 0 .
Mol.wt. 5 2 1 .
M.P.
86-89°C.
I t i s a i r stable.
I ti s
s o l u b l e i n a c e t o n e , i n s o l u b l e i n Et0H,Me0H.
( i i ) Epibromohydrin
Trithiazyl trichloride
( 0 . 9 0 g ) was t a k e n i n a S c h l e n k
and e p i b r o m o h y d r i n ( 6 m l ) added a t room t e m p e r a t u r e .
Immediately
the s o l u t i o n turned green which s l o w l y changed t o a p a l e - y e l l o w
l i q u i d a f t e r about a n h o u r .
The s o l u t i o n was s t i r r e d
f o r 20-24
h o u r s a t room t e m p e r a t u r e and a r e d s o l u t i o n was
obtained.
E x c e s s o f e p i b r o m o h y d r i n was removed by pumping,
and a r e d o i l
was o b t a i n e d .
Dry p e n t a n e ( 1 0 m l ) added t o t h e above o i l and t h e
s o l u t i o n was s t i r r e d
f o r a n h o u r , p e n t a n e was removed by
and a y e l l o w - w h i t e p r e c i p i t a t e was o b t a i n e d .
washed i n e t h a n o l and a f i n e powdery
vacuo a t room t e m p e r a t u r e .
Br=38.30, C l = 1 4 . 9 6 ; S . ^
suction
The p r e c i p i t a t e
was
s o l i d was formed and d r i e d i n
Found: S=13.55, N=7.40, C=16.30, H=2.16,
(O-CHg-CH Q. .CHgBr)^ r e q u i r e s , S=14.65, N=6.41,
C=16.48, H=2.23, C l = 1 6 . 2 5 , B r = 3 6 . 5 8 .
t h e o r y 655.34.
It i s a i r stable.
M.P.92-94°C, M o l . w t . i n benzene 6 4 4 ;
-81-
Ethylene
oxide
Trithiazyl trichloride
( 1 . 0 g ) was p l a c e d i n a S c h l e n k
o
and e t h y l e n e o x i d e was condensed
m i x t u r e was s l o w l y warmed
on i t a t -196 C.
t o room t e m p e r a t u r e .
The
A green
reaction
solution
was o b t a i n e d i m m e d i a t e l y w h i c h changed t o a p a l e y e l l o w l i q u i d
after
2 hours.
The l i q u i d was s t i r r e d and f i n a l l y a r e d s o l u t i o n
was o b t a i n e d a f t e r
24 h o u r s .
The e x c e s s o f e t h y l e n e o x i d e was
removed by pumping a t room t e m p e r a t u r e and a r e d o i l was o b t a i n e d .
Dry hexane ( 1 0 m l ) was added t o t h e o i l and t h e s o l u t i o n
stirred
f o r 12 h o u r s .
o i l was l e f t
behind.
Hexane was removed under s u c t i o n and a r e d
Found: S=24.00, N=11.30, 01=27.14, C=19.96,
H=3.06, ( N S C 1 . 0 . C H C H )
2
C=19.2, H=3.18.
was
2
3
requires:
S=25.48, N=11.15,
Mol. w t . 376 i n b e n z e n e .
Cl=28.27,
The r e d o i l
became d a r k r e d a t 50-60°C, p r o b a b l y due t o d e c o m p o s i t i o n .
It
decomposed t o a y e l l o w p r o d u c t i n a i r .
Butylene oxide
Trithiazyl trichloride
and about
( 1 . 8 g ) was p l a c e d i n a S c h l e n k
10 ml o f b u t y l e n e o x i d e added a t room t e m p e r a t u r e .
Immediately t h e s o l u t i o n
reaction after
5 minutes.
t u r n e d g r e e n and t h e r e was v i g o r o u s
T h e s o l u t i o n was s t i r r e d f o r 14 h o u r s
and a r e d l i q u i d was o b t a i n e d .
The e x c e s s b u t y l e n e o x i d e
was removed by pumping and a r e d o i l y p r o d u c t was o b t a i n e d .
Found: S=20.2, N,9.55, 01=22.70, C=31.33, H=5.11; SgN^O-CHg-ClCH -CH )
2
It
3
3
r e q u i r e s , S.20.84, N,9.12, 01=23.11, C=31.25 H=5.20.
decomposed t o a y e l l o w p r o d u c t i n a i r .
-82-
R e a c t i o n between t r i t h i a z y l t r i c h l o r i d e and p h e n y l a c e t y l e n e
Trithiazyl trichloride
( 0 . 5 g ) was c o o l e d t o -196°C and
p h e n y l a c e t y l e n e was condensed
warmed t o room t e m p e r a t u r e .
initially
on i t .
The r e a c t i o n f l a s k was
T h e r e was a v i g o r o u s r e a c t i o n
and g r e e n , p a l e - y e l l o w t o r e d c o l o u r change was
observed.
A red oily
was n o t i n v e s t i g a t e d
s t i c k y mass was o b t a i n e d .
The r e a c t i o n
further.
R e a c t i o n between t r i t h i a z y l t r i c h l o r i d e and d i p h e n y l a c e t y l e n e
Trithiazyl
trichloride
( 1 . 4 5 g ) was d i s s o l v e d
i n dry C C 1
4
(45 ml)
and d i p h e n y l a c e t y l e n e ( 1 . 2 g ) added a t room t e m p e r a t u r e .
s o l u t i o n was s t i r r e d
f o r 6 h o u r s a t room t e m p e r a t u r e , b u t no
o b v i o u s r e a c t i o n was o b s e r v e d .
18 h o u r s a t 42°C.
The s o l u t i o n was s t i r r e d f o r
The l i q u i d was changed
t o a g r e e n c o l o u r and
a y e l l o w p r e c i p i t a t e came o u t o f t h e s o l u t i o n .
was f i l t e r e d ,
The p r e c i p i t a t e
e v a p o r a t e d t o d r y n e s s and a m i x t u r e o f a r e d o i l
and a y e l l o w p r o d u c t was o b t a i n e d .
i n methylene
The
The p r e c i p i t a t e was washed
c h l o r i d e and pumped d r y a t room t e m p e r a t u r e .
The
i n f r a r e d s p e c t r u m o f t h e compound was i n d e n t i c a l w i t h t h e i . r . o f
S N C1.
4
3
Found: C l = 1 7 . 3 8 , S ^ g C l r e q u i r e s ; C l = 1 7 . 2 4 .
The
m i x t u r e o f t h e r e d o i l and t h e y e l l o w compound was i g n o r e d .
-83-
R e a c t i o n between t r i t h i a z y i
t r i c h i o i - i d e and c a r b o n monoxide
T r i t h i a z y l t r i c h l o r i d e ( 2 . 0 g ) was
C C l ^ ( 5 0 m l ) a t room t e m p e r a t u r e .
dissolved
i n dry
C a r b o n monoxide was
bubbled
t h r o u g h t h e s o l u t i o n a t a v e r y s l o w r a t e a t room t e m p e r a t u r e ,
f o r 48 h o u r s .
The s o l u t i o n was
p a l e - y e l l o w w h i t e p r e c i p i t a t e was
indicated
obtained.
t h a t S ^ N ^ C l ^ had undergone no
I n another experiment
higher temperature.
of
e v a p o r a t e d t o d r y n e s s and a
change.
t h e r e a c t i o n was
Carbon
The i . r . s p e c t r u m
monoxide was
c a r r i e d out a t
bubbled
through a
t r i t h i a z y l t r i c h l o r i d e ( 2 . 0 g ) i n 50 ml o f dry C C 1
solution
at
4
(2)
40 C f o r 60 h o u r s .
A y e l l o w p r e c i p i t a t e came out o f t h e
s o l u t i o n and t h e c o l o u r o f t h e s o l u t i o n was
p r e c i p i t a / e ^ was
filtered,
(2)
and a y e l l o w compound was
compound n o . l was
t h e f i l t r a t e was
obtained.
The
evaporated to dryness
i . r . spectrum
of
s i m i l a r t o S^N^Cl w h i l e t h e i . r . s p e c t r u m
of t h e compound no.2 was
i d e n t i c a l w i t h the product obtained
by p a s s i n g c h l o r i n e
vigorously
in CC1 .
72)
4
The
pale red.
( S e e page
R e a c t i o n between t r i t h i a z y l
through a s o l u t i o n of S N C I
t r i c h l o r i d e and
nitriles
Acetonitrile
S„N C I
( 2 . 0 g ) was
p l a c e d i n a S c h l e n k and
a c e t o n i t r i l e added a t room t e m p e r a t u r e .
for
12-14
h o u r s a t room t e m p e r a t u r e .
was
changed
15 ml o f dry
The s o l u t i o n was
The c o l o u r o f t h e
t o g r e e n , t h e n t o p a l e y e l l o w and f i n a l l y
stirred
solution
to red.
-84-
E x c e s s o f a c e t o n i t r i l e was removed by pumping a t room t e m p e r a t u r e .
A c r u d e b l a c k mass was o b t a i n e d .
The r e a c t i o n was n o t i n v e s t i g a t e d
further.
Propionitrile
Trithiazyl
dry
t r i c h l o r i d e ( 2 . 5 g ) was t a k e n i n a S c h l e n k and
p r o p i o n i t r i l e ( 1 2 - 1 5 m l ) added a t room t e m p e r a t u r e .
The
s o l u t i o n was t u r n e d g r e e n a f t e r 5-10 m i n u t e s , w h i c h s l o w l y
to p a l e y e l l o w .
The s o l u t i o n was s t i r r e d
a r e d l i q u i d was o b t a i n e d .
sticky
o i l was o b t a i n e d .
changed
f o r 12-14 h o u r s and
The l i q u i d was pumped and a r e d
The r e a c t i o n was n o t s t u d i e d
further.
Isobutyronitrile
Dry
i s o b u t y r o n i t r i l e ( 1 5 m l ) was added t o t r i t h i a z y l
trichloride
(1.8 g) i n a Schlenk.
T h e r e was no i m m e d i a t e
reaction.
The c o l o u r o f t h e s o l u t i o n was changed t o g r e e n ,
t h e n t o y e l l o w and a t t h e end, a f t e r 12-14 h o u r s a r e d o i l was
obtained.
was
The s o l u t i o n was pumped and a b l a c k c r u d e mass
obtained.
The r e a c t i o n was n o t i n v e s t i g a t e d
further.
Tertiarybuty1 cyanide
Dry
(1.8
t e r t i a r y b u t y l c y a n i d e ( 1 0 m l ) was added t o
g ) a t room t e m p e r a t u r e i n a S c h l e n k .
S^^Cl^
The s o l u t i o n was s t i r r e d
f o r 24 h o u r s and no o b v i o u s r e a c t i o n was s e e n t o t a k e p l a c e .
reaction
The
t e m p e r a t u r e was r a i s e d t o 58°C and t h e s o l u t i o n was
stirred
f o r 10 h o u r s .
A v e r y s m a l l amount o f y e l l o w p r e c i p i t a t e
(No.l)
was formed and t h e c o l o u r o f t h e s o l u t i o n was r e d .
-85-
The p r e c i p i t a t e was f i l t e r e d , f i l t r a t e was e v a p o r a t e d t o
d r y n e s s and g o l d e n y e l l o w (No.2) p r e c i p i t a t e was o b t a i n e d
(M.P. 240°C decomp.)
The i n f r a r e d s p e c t r u m o f ( N o . l )
p r e c i p i t a t e was r e c o r d e d , but t h e r e was i n s u f f i c i e n t sample o f
t h i s compound f o r f u r t h e r i n v e s t i g a t i o n s .
The compound (No.2)
was a n a l y s e d t w i c e .
Found: 1 s t . a n a l y s i s i n t h i s d e p a r t m e n t .
C = 28.90, H=3.79, C l = 3 3 . 1 0 , S=31.85, N = l l , 3 7 .
2nd, a n a l y s i s
( W e i l e r and S t r a u s s ) .
C=29.39, H=4.34, C l = 1 6 . 2 5 , S=26.55, N=9.37.
S
N
2 2
C 1
2^
C H
S N C (CH
)
3 3
C 1
r e c
u i r e s
»
C=30.56, H=4.58, C l = 1 8 . 0 0 ,
S=32.59,
14.26;
requires,
C=25.86, H=3.88, C l = 3 0 . 6 0 ,
S=27.58, N=12.04;
S_N_C_(CH„0„C1„ r e q u i r e s ,
C=24.39, H=3.66, C l = 2 8 . 8 6 ,
S=26.02, N=17.07.
£
Ct
£i £i
o
£t
) CI
*
O
O
O
&
O
The i n f r a r e d
A
s p e c t r u m o f compound ( N o . l ) showed t h e f o l l o w i n g
1227w, 1163 ms, 1000 s , 889 s , 858 s , 803 vw,
680 s , 607 vw,
The i n f r a r e d
1399 vw
943 w,
565 s , 554 s , 525 vw,
( 7 3 3 5 s , 722 s ) ,
466 v s , 451 vw ( s h ) .
s p e c t r u m o f compound (No.2) showed p e a k s a t : 1667
( s h ) , 1368 v s ( s h ) , 1274 w, 1222 s , 1087 w,
909 w,
885 v s , 855 s , 803 ms,
551 v s , 522 vvw,
288 vw,
peaks:
253 w,
733 s , 722 vvw
510 ms, 476 ms, 407 ms, 379 vw,
226 w cm
1
1019 w,
980
( s h ) , 590
341 w,
w,
308
vw,
vvw,
w,
.
Trichloroacetonitrile
S N CI
( 2 . 4 5 g ) was p l a c e d i n a S c h l e n k and dry t r i c h l o r o a c e t o n i t r i l e
(15 m l ) added a t room t e m p e r a t u r e .
stirred
The r e a c t i o n
mixture
was
f o r 24 h o u r s a t room t e m p e r a t u r e , and a y e l l o w s o l u t i o n
was
-86-
obtained.
The
l i q u i d was
y e l l o w p r e c i p i t a t e was
precipitate
indicated
evaporated
obtained.
t o d r y n e s s and
The
i n f r a r e d spectrum
t h a t S ^ N ^ C l ^ had undergone n©
I n another experiment,
stirred
f o r 2-3
of
days a t 60°C.
The
and
the
change.
t r i c h l o r o a c e t o n i t r i l e (10 ml)
added t o S ^ N ^ C l ^ ( 2 , 5 g) a t room t e m p e r a t u r e
was
a pale
the
was
solution
s o l u t i o n was
changed
t o g r e e n a f t e r about 1 h o u r , t h e n t o p a l e y e l l o w a f t e r about
2 h o u r s , and
was
finally
a r e d s o l u t i o n and
o b t a i n e d a f t e r 14 h o u r s .
The
a yellow
precipitate
precipitate
(No.l)
f i l t e r e d , washed i n t r i c h l o r o a c e t o n i t r i l e ( 5 m l ) and
The
f i l t r a t e was
(No.2) was
was
evaporated
obtained.
The
t o d r y n e s s and
compound (No.2) was
dried
a pale yellow
compound ( N o . l ) was
i n s u f f i c i e n t compound f o r f u r t h e r
was
a n a l y s e d t w i c e , i n t h i s department.
SgN C C I
01=55.04, S=24.80, N=10.85; S g N ^ C l
S=21.81, N=9.54; S g N ^ C l g
760
vw,
1047
676
analysis,
requires;
vvw
i n moist
air.
(sh),
v s , 543 v s , 535 ms
855 v s , ( 8 1 3 w
( s h ) , 517 w,
495
_1
471 w ( s h ) , 406 ms,
376
vw,
347 ms,
0=9.53,
0=8.19, 01=60.34,
I n f r a r e d a b s o r p t i o n s o c c u r a t : 1299
v s , 930 ms, 909
s , 722 vvw,
Found:
0=7.81, 01=57.72, S=20.81, N=13.66.
compound changed t o a w h i t e p r o d u c t
decomp. above 110°C.
1266
requires,
requires,
there
The
1 s t a n a l y s i s , 0=9.59, 01=55.89, S=24.75, N=11.60; 2nd.
The
precipitate
ignored because
investigations.
0=9.99, 01=52.80, S=21.98, N=10.51.
i n vacuo.
246
s , 225 vw cm
..
M.P.
vw,
( s h ) , 794 v s ) ,
vw
( s h ) , 483
s,
-87-
Benzonitrile
Trithiazyl
t r i c h l o r i d e ( 3 . 0 g ) was p l a c e d i n a S c h l e n k
was
and d r y b e n z o n i t r i l e / ( 2 0 m l ) added a t room t e m p e r a t u r e .
The
s o l u t i o n was s t i r r e d , a g r e e n c l e a r s o l u t i o n was o b t a i n e d a f t e r
10-15 m i n u t e s , w h i c h s l o w l y changed
2 hours.
to a pale yellow l i q u i d after
The s o l u t i o n was c o n c e n t r a t e d t o 10 ml and c o o l e d t o
o
0 C.
A p a l e y e l l o w p r e c i p i t a t e was o b t a i n e d .
spectrum of the p r e c i p i t a t e i n d i c a t e d
no
that SJ
The i n f r a r e d
C I , had undergone
change.
I n another experiment
S c h l e n k clamped
t h e r e a c t i o n was c a r r i e d o u t i n a
in a slightly
slanting position.
Benzonitrile
(25 m l ) added t o t r i t h i a z y l t r i c h l o r i d e ( 3 . 0 g ) a t room
temperature.
The s o l u t i o n was s t i r r e d a t 60°C.
solution
Immediately a green
was formed, t h e s o l u t i o n t u r n e d y e l l o w a f t e r 15 m i n u t e s .
S t i r r i n g was c o n t i n u e d and t h e s o l u t i o n was r e d a f t e r 4 h o u r s .
After
3-4 days a b r i g h t
y e l l o w p r e c i p i t a t e ( N o . l ) was s e t t l e d
down t h e r e d l i q u i d and b r i g h t
c o l l e c t e d near the f r i t
y e l l o w - o r a n g e n e e d l e s (No.2)
of the Schlenk.
The r e d s o l u t i o n
was c o o l e d t o -196°C and t h e y e l l o w - o r a n g e compound
pumped d r y a t room t e m p e r a t u r e .
After
removing
(No.2)
t h e compound
( N o . 2 ) , t h e r e d s o l u t i o n was warmed t o room t e m p e r a t u r e and t h e
y e l l o w p r e c i p i t a t e was f i l t e r e d , t h e r e d f i l t r a t e was c h i l l e d t o
(No.3)
0 C and f i n e y e l l o w n e e d l e s came out o f t h e s o l u t i o n .
The
-88-
s o l u t i o n was t r a n s f e r r e d
t o a 50 ml two-necked round bottomed
f l a s k and p r e c i p i t a t e (No.3) was f i l t e r e d ,
evaporated
t h e f i l t r a t e was vacuum
t o d r y n e s s and a d a r k y e l l o w compound (No.4) was
obtained.
T h e compound (No,4) was r e c r y s t a l l i s e d
or CHgClg.
from d r y C C l ^
The compound ( N o . l ) was d r i e d under v a c u o .
of t h e compound ( N o . l ) (about 0.5 g ) was d i s s o l v e d
of hot b e n z o n i t r i l e
filtered, chilled
were o b t a i n e d .
Some
i n about 20 ml
(60°C) and a r e d s o l u t i o n was o b t a i n e d ,
t o 0°C and f i n e y e l l o w n e e d l e s
The i n f r a r e d s p e c t r a
(N»^l and same a s No.3)
o f t h e compounds (No.1,2 and
No.3) w e r e i d e n t i c a l and a n a l y s e s showed t h a t
t h e two compounds a r e
t h e same.
Compound (No.1)
Found: C=41.72, H=2.55, C l = 1 4 . 9 2 , S=26.5, N=14.22;
S J
C H CI requires:
C=38.80, H=2.31, C l = 1 6 . 4 0 , S=29.56, N=12.93.
Compound (No.2)
Found: C=32.10, H=1.58, C l = 2 0 . 4 8 , S=30.56, N=14.68.
S
N
2 2
C 1
C
H
r
2 7 5
e
c
u
t
i
r
e
s
:
C=31.6, H=1.89, C l = 2 6 . 6 4 , S=24.09, N=15.79.
Compound (No.3)
Found: C=31.2, H=1.14, C l = 2 2 . 8 3 , S=29.73, N=16.60.
Compound (No.4)
Found: C=23.42, H=1.12, C l = 2 8 . 1 0 , S=24.15, N=16.33.
S
N
3 3
C
1
3
,
N=16.11.
P
h
C
N
r e (
l
u i r e s
»
C=24.18, H=1.45, C l = 3 0 . 5 9 , S=27.67,
-89-
I n f r a r e d s p e c t r a showed t h e f o l l o w i n g p e a k s :
Compound ( N o . l )
1660 w, 1290 v w ( s h ) ,
1212 vw, 1170 vw,
1149 s , 1070 w, 1029 ms, 1000 vw, 935 vvw, 921 s , 892 v s , 834 v s ,
794 s , 781 s , 767 s , 707 w ( s h ) , 699 v s , 662 v w ( s h ) , 548 v s , 515
-1
ms. cm
.
Compound (No.2 and 3 )
1600 w, 1350 vw ( s h ) , 1299 vvw,
1266 vvw, 1212 vvw. 1176 vvw, 1155 s , 1074 w, 1031 ms, 1002 vw,
943 vvw, 926 s , 897 v s , 844 v s , 787 s , 699 v s , 664 vw, 549 v s . cm
Compound (No.4)
1590 ms, 1290 w ( s h ) , 1179 s , 1093 w,
1065 w, 1022 ms, 998 vvw ( s h ) , 910 v s , 870 vvw ( s h ) , 842 vvw ( s h ) ,
791 v s , 662 ms, 615 vvw, 525 s , 493 v s , 473 s . cm
1
.
DISCUSSION
-90-
T e t r a s u l p h u r t e t r a n i t r i d e adducts w i t h Lewis
acids
T e t r a s u l p h u r t e t r a n i t r i d e r e a c t s w i t h many L e w i s
acids
( e . g . m e t a l h a l i d e s and SO^) t o g i v e compounds o f a v a r i e t y
of e m p i r i c a l c o m p o s i t i o n s .
I n i n e r t organic solvents,
adducts
of 2:1, 1:1, 1:2, 1:4 ( S ^ N ^ : L e w i s a c i d ) s t o i c h b m e t r y h a v e been
prepared, i n which
Lewis a c i d .
t h e n i t r o g e n o f S^N
i s co-ordinated to the
4
I n t h e s e a d d u c t s , t h e S.N
r i n g undergoes a
T:
c o n f o r m a t i o n a l change a s a r e s u l t o f d o n a t i o n o f e l e c t r o n s
n i t r o g e n and c o n s e q u e n t
The
from
w e a k e n i n g o f t h e s u l p h u r - s u l p h u r bond.
aims o f t h e r e s e a r c h were, t o f u r t h e r e x p l o r e t h e
r e a c t i o n s o f S^N^ a s a L e w i s b a s e , t o s t u d y t h e e f f e c t s o f
c o o r d i n a t i o n upon t h e r e a c t i v i t y
of the S N
4
4
r i n g and t o g a i n
more i n f o r m a t i o n about t h e s t r u c t u r e s o f t h e p r o d u c t s .
was
It
a l s o hoped t o c o r r e l a t e t h e v a r i o u s p r o p e r t i e s p r e v i o u s l y
noted
o f S^N,. and t h e s t r u c t u r e s o f t h e a d d u c t s .
4 4
We found t h a t
adducts
i n which
t i n t e t r a c h l o r i d e and t e t r a b r o m i d e gave
S,N, t o m e t a l h a l i d e r a t i o i s 2 : 1 : on t h e o t h e r
4 4
hand, t i n t e t r a i o d i d e , s i l i c o n t e t r a c h l o r i d e , germanium
and s t a n n o u s
tetrachloride
c h l o r i d e , gave no a d d u c t s under t h e c o n d i t i o n s s t u d i e d .
No s u i t a b l e s o l v e n t was found ( b e c a u s e o f i n s o l u b i l i t y
of SnF^
i n n o n - c o a r i i n a t i n g s o l v e n t s ) t o s t u d y t h e r e a c t i o n between S^N^
and
t i n tetrafluoride.
-91-
T i t a n i u m t e t r a b r o m i d e and t e t r a i o d i d e , Z r C l . . . H f C l . , SeCl...
*
4
4
4
TeCl , TeF
4
4 >
NbClg, NbFg, T a F
and W0C1
g
c o m p o s i t i o n , w h e r e a s A1C1 , A l B r
*3
, GaCl
J
( ? ) gave a d d u c t s o f 1:1
4
, InCl
*3
, T1C1 ( ? )
*j
&
and FeCl„ gave p r o d u c t s o f 1:2 s t o i c h b m e t r y .
In
t h e r e a c t i o n o f t u n g s t e n hexabromide w i t h S..N.,, t h e
4 4'
bromide was f i r s t
reduced
t o WBr. and gave t h e a d d u c t , S„N„.
4
' 4 4
WBr. ( a n a l o g o u s t o t h e r e a c t i o n o f S.N,, and WC1„ t o g i v e S.N..WC1.).
4
4 4
b
4 4 4
Phenylboron
dichloride reacted with S ^
4
to y i e l d the
a d d u c t S ^ ^ P h B C l g , w h e r e a s p - t o l y t i n t r i c h l o r i d e gave S n C l . 2 S N
4
due
4
to the disproportion of the p - t o l y t i n t r i c h l o r i d e to S n C l
and t e t r a - p - t o l y t i n .
by m i x i n g t h e s o l u t i o n s o f S N
4
4
prepared
and L e w i s a c i d s i n s o l v e n t s o f
low p o l a r i t y , u s u a l l y under a n atmosphere o f d r y n i t r o g e n .
The
r e a c t i o n m i x t u r e s were s t i r r e d
and t h e c o l o u r e d p r o d u c t s were
f i l t e r e d and d r i e d
The r e a c t i o n t i m e was found t o
i n vacuo.
depend on t h e s o l u b i l i t y
of the Lewis a c i d .
I n t h o s e c a s e s , where
L e w i s a c i d was s o l u b l e i n t h e s o l v e n t , t h e r e a c t i o n t i m e was
from 1-10 h o u r s
of
(until
t h e r e was no f u r t h e r change i n t h e c o l o u r
t h e p r o d u c t ) , whereas,
i f t h e L e w i s a c i d was o n l y
s o l u b l e i n t h e s o l v e n t , t h e p r o c e d u r e was t o add S N
4
suspension of the Lewis a c i d
for
4
F u r t h e r d e t a i l s a r e g i v e n i n T a b l e 1.
T e t r a s u l p h u r t e t r a n i t r i d e a d d u c t s were g e n e r a l l y
the
4
12-24 h o u r s o r l o n g e r .
i n t h e s o l v e n t and s t i r
4
slightly
to the
the solution
c
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PQ
-95-
I n some c a s e s , c h o i c e o f a s u i t a b l e s o l v e n t was found
the
i m p o r t a n t f a c t o r e . g . i t was p o s s i b l e t o p r e p a r e t h e S^N^
adduct
of aluminium
t r i b r o m i d e u s i n g t h e s o l v e n t s bromoform o r
carbon d i s u l p h i d e , but t h e r e a c t i o n of S N
4
or
t o be
t o l u e n e gave a n o i l y
instability
s t i c k y product.
and
A
Because
1
B
decomposes above 90 C
54
r
3
*
n
C
C
1
4
of thermal
o f many t e t r a s u l p h u r t e t r a n i t r i d e a d d u c t s
o
S.N ,BF
4
(e.g.
v
) most o f t h e r e a c t i o n s were
s t u d i e d between 0°-20°C.
Many a d d u c t s were s t a b l e under d r y n i t r o g e n a t m o s p h e r e f o r
s e v e r a l days b u t decomposed i n m o i s t a i r u s u a l l y g i v i n g
and
the h y d r o l y s i s product
of t h e Lewis
S N
4
4
acid.
138
The
electronegativity
d i f f e r e n c e between s u l p h u r
(2.44)
138
and n i t r o g e n ( 3 . 0 7 )
partial
i n t e t r a s u l p h u r t e t r a n i t r i c l e would
n e g a t i v e c h a r g e on n i t r o g e n atoms and p a r t i a l
c h a r g e on s u l p h u r atoms.
as
Consequently
e i t h e r a Lewis base through
cause
positive
t h e compound may a c t
t h e n i t r o g e n atoms o r a s a L e w i s
a c i d t h r o u g h t h e s u l p h u r a t o m s . S i n c e we have o n l y s t u d i e d
the r e a c t i o n s o f S.N. w i t h L e w i s a c i d s , t h e L e w i s b a s e b e h a v i o u r
4 4
'
of S N i s c o n s i d e r e d b e l o w .
^
134, 135, 136
.
^
.... ..
„
4
4
Recently
a r u l e concerning the s t a b i l i t y of
a c i d - b a s e c o m p l e x e s h a s been s u g g e s t e d "The P r i n c i p l e o f Hard and
S o f t A c i d s and B a s e s " o r HSAB p r i n c i p l e , w h i c h may be a p p l i e d t o
understand
t h e donor p r o p e r t i e s o f S N
4
4 >
-96-
According to t h i s r u l e , bases i n which
t h e donor atom
i s , N, 0, o r F ( i . e . o f h i g h e l e c t r o n e g a t i v i t y
and s m a l l s i z e )
a r e ( c l a s s i f i e d a s 'hard' b a s e s , e . g . NH ,H 0,0H , F ; and b a s e s
i n which
t h e donor atom i s P , S , I , B r , C l o r C a r e c a l l e d
'soft'
b a s e s , e . g . R^S, RgP> CN ; w h e r e a s t h e b o r d e r l i n e c a t e g o r y
takes i n t o account
such f a c t o r s a s , the presence of u n s a t u r a t i o n
i n some n i t r o g e n d o n o r s ,
which
s h o u l d l o o s e n up t h e v a l e n c y
e l e c t r o n s , e . g . CgHgNHg, C^H N.
o f h a r d and s o f t
From t h e above
b a s e s i t c a n be s e e n
u n s a t u r a t e d n i t r o g e n ) may f a l l
4
(containing
base).
t h e same way i t i s p o s s i b l e t o c l a s s i f y
( C l a s s A ) and s o f t
a c i d s , i n which
4
i n the borderline category ( i . e .
i n t e r m e d i a t e between a h a r d and s o f t
In exactly
that S N
classification
( C l a s s B) Lewis a c i d s :
hard
the C l a s s A Lewis
a c c e p t o r atoms a r e s m a l l i n s i z e o f h i g h
positive
c h a r g e and do n o t c o n t a i n u n s a t u r a t e d p a i r s o f e l e c t r o n s i n t h e i r
valency s h e l l
+
+
(e.g. H , L i ,
BFg); the C l a s s B Lewis
acids
g e n e r a l l y have a c c e p t o r atoms large/In s i z e , o f low p o s i t i v e
c h a r g e and c o n t a i n i n g u n s h a r e d
p a i r s of e l e c t r o n s
e l e c t r o n s ) i n t h e i r valency s h e l l
(p or d
+
+
+
+
( e . g . Hg , Cu , T l , RS ) .
For Lewis a c i d s the important p r o p e r t i e s that determine s o f t n e s s
a r e s i z e , c h a r g e o r o x i d a t i o n s t a t e , e l e c t r o n i c s t r u c t u r e and
135 ,
t h e n a t u r e o f t h e a t t a c h e d groups
adducts
later).
( f o r examples s e e S N
4
4
-97-
I n v i e w o f t h e above p r i n c i p l e
i t was i n t e r e s t i n g t o s t u d y
the v a r i o u s adducts o f t e t r a s u l p h u r t e t r a n i t r i d e w i t h
acids.
Lewis
I t was hoped t h a t any r a d i c a l d i f f e r e n c e s i n t h e s t r u c t u r e s
of t h e adducts
would be r e v e a l e d by i n f r a r e d s p e c t r a and c h e m i c a l
properties.
( a ) T e t r a s u l p h u r t e t r a n i t r i d e adducts
tin tetrachloride
The
formation
of s i l i c o n ,
o f t i n t e t r a b r o m i d e and
o f c o o r d i n a t i o n c o m p l e x e s by t h e t e t r a h a l i d e s
germanium and t i n w i t h p y r i d i n e and a c e t o n i t r i l e
(border-
l i n e b a s e s a c c o r d i n g HSAB p r i n c i p l e ) may be compared t o t h e
r e a c t i o n s o f S.N„ w i t h
4 4
The
observed
tetrahalides.
r a t i o s o f a c c e p t o r t o donor i n t h e s e a d d i t i o n
compounds a r e most f r e q u e n t l y 1:2 o r 1:1, more r a r e l y
1:4 and
137
occasionally
silicon,
r a t i o s other than these
germanium and t i n a p p e a r s
S i and F
CI
Br
.
The t e t r a h a l i d e s o f
to follow the acceptor
I .
sequence
Sn
Ge
I t c a n be s e e n from T a b l e 1
that
t h e r a t i o o f S„N. t o S n C l . and S n B r . i n t h e s e a d d u c t s i s
4 4
4
4
2:1,
w h e r e a s S i C l ^ , G e C l ^ form no a d d u c t s
w i t h S^N^.
From t h e
above o b s e r v a t i o n s we may a s s i g n i n c r e a s i n g s o f t n e s s i n t h e o r d e r
CHgCN ) ^ 4 4 y ^ 5 5
N
H
N <
T h i s appears
t o be r e a s o n a b l e s i n c e p y r i d i n e
forms a d d u c t s w i t h S i C l
G e C l and S n l
whereas i n t h e c a s e o f
CH„CN and S„N„, no a d d u c t f o r m a t i o n h a s b e e n r e p o r t e d o r o b s e r v e d
3
4 4'
with these h a l i d e s .
T e t r a s u l p h u r t e t r a n i t r i d e c a n be c o n s i d e r e d
4 >
4
4 >
as a s t r o n g e r base than a c e t o n i t r i l e , because t e l l u r i u m
tetrafluoride
-98-
and t h a l l i u m
solution
t r i c h l o r i d e form a d d u c t s w i t h S.N.
in acetonitrile
4 4
( e . g . c o n s i d e r the
i
acid-base substitution
i
B
+ A : B — ¥ AB
+ B,
if
the
goes a s
The
reaction
where B
atom.
considering
) >
B
'
b a s e s and
A
i s an
acid,
i s a stronger base than
s t a t e of h y b r i d i s a t i o n
donor s t r e n g t h
3
N(sp
B are
o f n i t r o g e n bases^'more s i m p l y
the
With r e g a r d to the
2
N(sp ) >
o
N CH CN = 180 .
and
indicated
r e l a t i v e donor a b i l i t y
e x p l a i n e d by
reaction,
i
^
n pyridine
( SD )
N(sp);
s
p
be
of the
donor
o f n i t r o g e n atoms,
9
9
3
A
; N S N
= 116°
2
K
135
B)
1
2
3
(
s
)
p
=
0
113°
o
(sP)
In t i n tetrahalides
SnCl^ y
and
the
S n B r ^ "y
Snl^
n a t u r e of
the
electronegativity
c h a r g e on
Sn
of
the
o r d e r of a c i d s t r e n g t h
i s SnF^
( f r o m s i z e , c h a r g e or o x i d a t i o n
||
state
a t t a c h e d g r o u p s ) , because the h i g h
138
f l u o r i n e (4.1)
leaves higher p o s i t i v e
i n S n F ^ t h a n on Sn
i n other t e t r a h a l i d e s
of
tin
138
(E.N.
are
values,
equal.
C l = 2 . 8 3 , Br=2.74, 1=2.21)
T h e r e f o r e i t i s not
complex w i t h S^N^. ( T h i s does not
t i n tetraiodide
reaction
has
not
a d d u c t i s not
and
other
s u r p r i s i n g t h a t S n l ^ gave
preparable.
I t may
be
I t i s generally
i n t e r m o l e c u l a r bonds o f
donor-acceptor type are
r e s u l t of charge t r a n s f e r
acceptor molecule.
s h o u l d be
that
been examined o v e r s u f f i c i e n t l y w i d e r a n g e
the
accepted
the
of
that
formed
from a donor m o l e c u l e t o
Consequently the p r o p e r t i e s
dependent upon t h e
no
n e c e s s a r i l y mean t h a t S^N^ -
experimental conditions).
the
factors
as
an
of donor bonds
d e g r e e of c h a r g e t r a n s f e r
from donor
to
-99-
acceptor
121
.
T h i s h a s been v e r i f i e d by e s t a b l i s h i n g the
r e l a t i o n s h i p between t h e d e g r e e o f c h a r g e
transfer
(from t h e
v a l u e o f t h e d i p o l e moment o f t h e i n t e r m o l e c u l a r b o n d s ) and
122
the s t a b i l i t y
( f r o m t h e h e a t o f complex f o r m a t i o n
of a m e t a l - l i g a n d bond i s most s a t i s f a c t o r i l y
enthalpy
change,
).
Strength
defined as the
£ H , accompanying t h e g a s - p h a s e
dissociation
118
o f t h e complex
.
Sometimes however, t h i s
information
i s n o t a v a i l a b l e and t h e s t r e n g t h o f t h e donor a c c e p t o r bond i s
estimated
from t h e magnitude o f t h e s t a b i l i t y
constant, which i s
118
t h e e q u i l i b r i u m c o n s t a n t , Kp, f o r t h e r e a c t i o n
:
D ( g ) + M X ( g ) ^ = i D.MX (g)
3
3
D=donor, M=metal, X=halogen
When e q u i l i b r i u m c o n s t a n t s a r e used
c a r e h a s t o be t a k e n
i n interpreting
as a c r i t e r i o n of s t a b i l i t y
the r e s u l t s .
T h i s i s because
e q u i l i b r i u m c o n s t a n t s a r e a measure o f a f r e e e n e r g y change, n o t
o
the r e q u i r e d enthalpy
change,
£ G •= - R t l n . K p .
Therefore,
i f Kp f o r one a d d i t i o n compound i s g r e a t e r t h a n f o r a s e c o n d a t
a given temperature,
i t does n o t n e c e s s a r i l y
follow that the
d i s s o c i a t i o n o f t h e former i s accompanied by t h e s m a l l e r
change.
T h i s i s only t r u e i f the entropy
both r e a c t i o n s i s v e r y s i m i l a r .
of d i s s o c i a t i o n i n
A s i n d i c a t e d above, t h e most
s a t i s f a c t o r y method o f i n v e s t i g a t i n g t h e s t a b i l i t y
i s by s t u d y i n g t h e g a s p h a s e
i t s component p a r t s .
enthalpy
o f an a d d u c t
d i s s o c i a t i o n o f t h e compound i n t o
A knowledge o f how t h e d e g r e e o f d i s s o c i a t i o n
-100-
v a r i e s with temperature
and
p e r m i t s t h e thermodynamic f u n c t i o n s ,
t o be c a l c u l a t e d and
t h i s enables a
quantitative
measure of t h e s t r e n g t h of t h e m e t a l - l i g a n d bond t o be
The
e x p e r i m e n t a l techniques for s t u d y i n g gas-phase
obtained.
dissociation
of m o l e c u l a r a d d i t i o n compounds have been d e v e l o p e d
by Brown,
118
T a y l o r and G e r s t e i n
.
The
gas-phase
dissociation
f o r t h e s t u d y o f a d d i t i o n compounds h a s c e r t a i n
Thus i t i s d i f f i c u l t
limitations.
t o s t u d y i n t h e gas p h a s e a d d u c t s w h i c h
a l r e a d y a t t a i n e d a h i g h degree
above s a t u r a t i o n p o i n t .
The
of d i s s o c i a t i o n a few
d i s s o c i a t i o n method i s a l s o
d i s s o c i a t i o n at a convenient
do not
molecular
a d d i t i o n compounds have been e s t a b l i s h e d by d i s p l a c e m e n t
2 2
,54
(e.g. S N .BF + BC1
> S ^ . B C l g + BF^) .
4
I t has
4
3
give
temperature.
I n many i n s t a n c e s t h e r e l a t i v e s t a b i l i t i e s o f
C H
have
degrees
u n s u i t a b l e f o r t h e s t u d y of complex compounds w h i c h
a measurable
technique
reactions
C 1
3
l o n g been customary
t o i n f e r o r d e r s of r e l a t i v e
stability
118
from measurement o f s a t u r a t i o n p r e s s u r e
for
two a d d i t i o n compounds of c l o s e l y
weight
the l e s s s t a b l e e x h i b i t s
( e . g . t h e o r d e r of s t a b i l i t y ,
.
As a g e n e r a l r u l e
similar
t y p e and
molecular
the h i g h e r s a t u r a t i o n p r e s s u r e
(CHg^N.BFg >
(CH ) N.BCCH ) ;
3
3
3
3
118
the order of s a t u r a t i o n p r e s s u r e ( C H ) N . ( B C H >
3
F o r a d d i t i o n compounds d i f f e r i n g
expected
3
3
3
(CHg) .BF )
g
i n molecular weight
t h a t t h e l i g h t ^ e r would be more v o l a t i l e
S.N..BF ) .
>
g
i t i s to
be
( e . g . S^N^.BClg
I f however t h e h e a v i e r complex i s found t o be more
-lOr
v o l a t i l e ^ t h i s i s taken to i n d i c a t e that
highly
i t i s a l s o more
dissociated.
It
i s possible
to consider
the existence
of a
coordination
138
complex i n terms o f an e n e r g y c y c l e
and t h e c y c l e c a n be
u s e d q u a l i t a t i v e l y f o r d i s c u s s i o n o f r e a l o r p o s s i b l e compounds.
It
s h o u l d be u n d e r s t o o d t h a t e v e r y d o n o r - a c c e p t o r r e a c t i o n
requires
adjustment o f energy l e v e l s i n r e l a t i o n t o each o t h e r t o a c c o r d
with the actual properties
t h e a d j u s t m e n t energy
of the system.
(or reorganisation
I n some
instances
e n e r g y ) may be
greater
t h a n t h e e n e r g y r e l e a s e d by d a t i v e - b o n d f o r m a t i o n s o t h a t
there
i s no c o m b i n a t i o n , t h e g a s - p h a s e f r e e e n e r g y o f f o r m a t i o n b e i n g
p o s i t i v e instead of negative.
o f t h o s e extreme c a s e s
acceptors
T h i s may w e l l be t r u e f o r some
where no r e a c t i o n t a k e s
place
between
and donors h a v i n g l a r g e alkyl groups a t t a c h e d
t o them.
On t h e o t h e r hand, from t h e k i n e t i c s o f c o o r d i n a t e bond
formation
i n t h e vapour p h a s e , t h e e n e r g y o f r e a d j u s t m e n t f o r r e a c t i o n s
between some c l a s s e s o f donor and a c c e p t o r c a n be q u i t e
This
small.
i s t r u e f o r complex compound f o r m a t i o n between c e r t a i n
amines and boron h a l i d e s .
A l t e r n a t i v e l y , t h e Donor.MX
standard
o
s t a t e may l i e above t h e (MX
a d d u c t would n o t form.
Thus w i t h r e s p e c t
+ D) s t a n d a r d s t a t e s s o t h a t t h e
A l l these
energy s t e p s
a r e complex.
t o t h e a c i d , adjustment f o r bonding
involves
e n e r g y o f r e h y b r i d i s a t i o n o f t h e m e t a l atom t o g i v e t h e
required
coordination
number, e . g . i n t h e c a s e
of S n C l . to g i v e an
-102-
o c t a h e d r a l c o o r d i n a t i o n ( r e d u c t i o n i n bond a n g l e s
to approximately
90°).
bonding between M and
more c o s t l y
from 109^28'
Sometimes t h e e x i s t e n c e o f
X i n MX^ makes t h i s s t e p
energetically
t h a n i n o t h e r s i t u a t i o n s where s u c h
l e s s or a b s e n t ,
( e . g . S ^ N ^ B C l ^ i s more s t a b l e t h a n
R e h y b r i d i s a t i o n c o n s i d e r a t i o n s a l s o apply
of base although
bonding i s
S^N^.BF^).
to the
molecules
u s u a l l y t h e c h a n g e s a r e not a s d r a s t i c
i n t h e c a s e of a c c e p t o r s .
the acceptor molecule
as
A further complication occurs i f
e x i s t s as a polymer.
Then c o n v e r s i o n
o f MXg ( s t a n d a r d s t a t e ) t o MXg(g) r e q u i r e s e n e r g y f o r
d e p o l y m e r i s a t i o n ( e . g . complex f o r m a t i o n
by d i m e r i c
h a l i d e s i n s o l u t i o n or by s o l i d h a l i d e s p o l y m e r i s e d
halogen b r i d g e s ) .
through
Thus from t h i s b r i e f c o n s i d e r a t i o n of
energy s t e p s i n complex compound f o r m a t i o n ,
that
aluminium
i t i s readily
the
seen
i t i s impossible to a s s i g n d e f i n i t e s t r e n g t h s to e l e c t r o n -
ic
p a i r donors and
acceptors v a l i d
S i n c e many S^N^ a d d u c t s
i n i n e r t o r g a n i c s o l v e n t s , any
for every acid-base r e a c t i o n
a r e i n s o l u b l e or s l i g h t l y
soluble
p h y s i c a l measurements s u c h
vapour p r e s s u r e , d i p o l e moment e t c . would be d i f f i c u l t .
i n t h o s e c a s e s where t h e a d d u c t s
as
However,
are soluble i n i n e r t s o l v e n t s ,
i t may be p o s s i b l e t o g a i n more knowledge about t h e p r o p e r t i e s
o f S„N. a d d u c t s .
The a d d u c t S.N..4SbF, a p p e a r s t o be l e s s
4 4
4
4
o
s t a b l e t h a n S.N .SbCl
o f S„N..4SbF.. i n m o i s t
4 4
3
, because of the very r a p i d
air.
T h i s behaviour
may
decomposition
be e x p l a i n e d i n
-103tersr.s o f two e f f e c t s
nitrogens of S N
( i ) t h e d o n a t i o n o f e l e c t r o n s from one o f t h e
c a u s e s t h e w e a k e n i n g o f t h e donor a b i l i t y o f
t h e o t h e r n i t r o g e n atoms.
Consequently,
m o l e c u l e s w i l l be a t t a c h e d more w e a k l y
S^N^.SbF,. and p r o b a b l y more w e a k l y
t h e antimony
pentafluoride
than i n ( h y p o t h e t i c a l )
t h a n i n S^N .SbCl,..
Rapid
4
h y d r o l y s i s o f S^N^.4SbFg i n m o i s t a i r i s t h e r e f o r e t o be e x p e c t e d ,
( I i ) Steric
effect:
a s t h e adduct
g e t s b i g g e r i t may become
less
stable.
The
c a s e with which
the S N
4
4
a d d u c t s undergo h y d r o l y s i s
i n m o i s t a i r c a n be c o n s i d e r e d i n terms o f HSAB p r i n c i p l e and may
i n t u r n probably e x p l a i n t h e i r s t a b i l i t i e s .
the S N
4
Thus s i n c e
i s a v e r y s t r o n g donor, n o r t h e S n C l
4
4
neither
i s a strong acceptor,
i n t h e a d d u c t . 2S„N..SnCl„ both S.N. and S n C l . may be c o n s i d e r e d
' 4
4
4
4 4
4
J
as n e a r l y matching
the adduct
p a r t n e r s and c o n s e q u e n t l y one would e x p e c t
t o be r e l a t i v e l y
decomposition
stable.
of 2S N .SnCl
4
4
4
T h i s i s siown by t h e s l o w
i n moist a i r .
F u r t h e r t h e same
argument c a n be a p p l i e d t o e x p l a i n t h e s t a b i l i t i e s
and S _N„ .SbCl,. a d d u c t s where t h e l a t t e r a p p e a r s
4 4
5
than S N . B C 1
4
4
3 >
4
4
5
3
4
N
4
•BCl.j
t o be more s t a b l e
s i n c e S N . S b C l , . c a n be o b t a i n e d from t h e a d d u c t ,
4
4
o
S N .SbCl .BCl
of S
54
a t 85-90 C.
partner or acceptor f o rS N
4
Thus S b C l
4
than BClg
.
5
would be a b e t t e r
matching
However, i t i s s t i l l
q u i t e p o s s i b l e f o r a compound formed from a h a r d a c i d and a s o f t
135
t o be more s t a b l e t h a n one made from a b e t t e r matched p a i r
.
base
-104-
(b) T e t r a s u l p h u r t e t r a n i t r i d e adducts of t i t a n i u m ,
and h a f n i u m t e t r a h a l i d e s
Titanium
zirconium
t e t r a c h l o r i d e , tetrabromide, t e t r a i o d i d e , zirconium
t e t r a c h l o r i d e and h a f n i u m t e t r a c h l o r i d e , form 1:1 a d d u c t s
N
^4 4*
From e l e c t r o n e g a t i v i t y c o n s i d e r a t i o n s T i C l ^ would be a
better acceptor
Sn^
with
+
= O.TiK,
f o r S^N^ t h a n S n C l ^ ( t h e e s t i m a t e d
Ti^
+
ionic
radii,
= 0 . 6 8 8 ) * ^ s i n c e n e u t r a l a c i d s and b a s e s
w i l l have s t r e n g t h p r o p o r t i o n a l t o t h e l o c a l d i p o l e s a t t h e
acceptor
not
do
o r donor e n d .
S i l i c o n t e t r a c h l o r i d e and G e C l ^ do
form a d d i t i o n compounds w i t h S^N^, a l t h o u g h
T i C l ^ and S n C l ^
s o ^ a d i f f e r e n c e w h i c h may be a t t r i b u t e d t o a b i l i t y
h a l o g e n atoms t o f i l l
t h e c o o r d i n a t i o n sphere
of the
of the smaller
S i and Ge a t o m s .
4+
of t h e Zr
Z i r c o n i u m t e t r a c h l o r i d e and H f C l ^ ( t h e r a d i i
and
Hf^
+
i o n s a r e 0.74 and 0.75 r e s p e c t i v e l y * ^ )
resemble
138
TiCl
i n t h e i r chemical p r o p e r t i e s
4
.
Similar considerations
c a n be a p p l i e d t o o t h e r h a l i d e s o f t h e g r o u p .
Titanium
tetrafluoride
gave t h e a d d u c t S ^ N ^ ^ T i F ^ , t h u s u s i n g a l l t h e f o u r b a s i c s i t e s
in
S N .
4
4
( c ) T e t r a s u l p h u r t e t r a n i t r i d e adducts o f boron, aluminium,
g a T l i u m , i n d i u m , t h a l l i u m and i r o n t r i h a l i d e s
As
p r e v i o u s l y m e n t i o n e d ( s e e page 11,91), B C l , BBr^, P h B C l g ,
g
form 1:1 a d d u c t s w i t h S N
4
N
£>4 4
, B F
3 and B F . 4 S N
g
4
4
4 f
w h e r e a s i n t h e c a s e o f B F 3 1 two a d d u c t s ,
have been r e p o r t e d .
However, t h e a d d u c t
-105-
B F . 4S N
appears
3
4 4
t o be u n u s u a l
s i n c e the i n a b i l i t y
t o have c o o r d i n a t i o n numbers e x c e e d i n g f o u r .
Aluminium
and t r i b r o m i d e G a C l g , I n C l g , and F e C l ^ gave 1:2
adducts
metal h a l i d e ) , w h i l e the stcfchiometry i n t h a l l i u m
adduct
of boron
trichloride
(S^^:
trichloride
i s n o t known.
I n BX
compounds t h e b o r o n o c t e t
i s incomplete; boron has
a l o w - l y i n g u n f i l l e d o r b i t a l , c o n s e q u e n t l y BX^ ( x = h a l o g e n ) compounds
behave a s L e w i s a c i d s
i n w h i c h boron a c h i e v e s i t s maximum
3
c o o r d i n a t i o n number w i t h a p p r o x i m a t e l y
sp
hybridisation.
T h e r e i s good e v i d e n c e t h a t t h e r e l a t i v e s t r e n g t h s o f t h e boron
h a l i d e s as Lewis a c i d s a r e i n the order B B r
3
}
B
C
1
B F
3 ^
T h i s o r d e r i s o p p o s i t e o f what would be e x p e c t e d b o t h
grounds and
from e l e c t r o n e g a t i v i t y c o n s i d e r a t i o n s .
be .explained a t l e a s t p a r t i a l l y
bonding.
3*
in steric
I t can
i n terms o f t h e boron
halogen
A c c e p t o r atoms a r e l e s s e f f e c t i v e when t h e v a c a n t
o r b i t a l c a n be a t l e a s t p a r t l y used i n m u l t i p l e b o n d i n g w i t h i n
140
the molecule
.
I n a n a d d i t i o n compound t h i s
TT b o n d i n g
is
l a r g e l y o r c o m p l e t e l y l o s t s o t h a t a d d i t i o n compounds o f t h e
boron t r i h a l i d e s w i t h t h e s t r o n g e s t TT b o n d i n g w i l l
most d e s t a b i l i s e d
through
l o s s of the
TT b o n d i n g
be
the
139
energy
138
Calculations
i n d i c a t e t h a t the TT b o n d i n g e n e r g i e s o f t h e
t r i h a l i d e s a r e i n the order B F >
^
3*
However
138
B
3
certain properties
C
1
B
B
r
3
o f t h e BX
a d d u c t s w i t h donor m o l e c u l e s
s u g g e s t t h a t t h e donor t o boron bonds may t h e m s e l v e s i n c r e a s e i n
s t r e n g t h i n t h e o r d e r BF~ <
BC1
< RBr
d
3
3.
T h i s may be
Q
D J 3 I
-106-
e x p l a i n e d by t h e a p p l i c a t i o n of t h e m u t u a l s t a b i l i s i n g
effect
141
c a l l e d symbiosis
( i . e . s o f t b a s e s t e n d t o group t o g e t h e r
on
a g i v e n c e n t r a l atom and h a r d l i g a n d s t e n d t o group t o g e t h e r ) .
I n BX
The
h a l i d e s boron i s f o r m a l l y i n a p l u s t h r e e o x i d a t i o n s t a t e .
hard F
l i g a n d s form a complex w h i c h
i s strongly ionic,
b o r o n atom i n B F ^ i s a p p r e c i a b l y p o s i t i v e and h a r d .
Thus t h e
p r e s e n c e of h a r d f l u o r i d e i o n i n B F ^ makes i t e a s y t o add
hard bases
other
( e . g . BF^.ORg i s more s t a b l e t h a n B F g . S F g ) .
a d d u c t s S N . B F g and S ^ ^ B C l g
4
the l a t t e r
4
the
In
i s more s t a b l e
the
(since
v54
BC1
3
r e p l a c e s B F ^ from S N
4
because
S N
4
4
4 <
BF
3
i n CH^l^
i s a b e t t e r matching
or the b e t t e r s t a b i l i t y
4
4
4
3
p a r t n e r f o r B C l ^ than f o r BF^
of S N . B C 1
4
to give S N .BC1 0
3
compared t o S N » B F
4
4
3
c a n be e x p l a i n e d by c o n s i d e r i n g BC1„ a s a b e t t e r a c c e p t o r t h a n
BF„.
Thus both t h e above e x p l a n a t i o n s c a n be u s e d t o e x p l a i n
o
the r e l a t i v e s t a b i l i t i e s
Aluminium and
of these adducts.
i t s congeners
Ga,
In, T l are considerably
l a r g e r t h a n boron ( a t o m i c r a d i i of A l and B b e i n g 1.26
r e s p e c t i v e l y ) and
and 0.88 A*
t h e i r t r i h a l i d e s behave a s L e w i s a c i d s
and
c a n a c c e p t e i t h e r n e u t r a l donor m o l e c u l e s
or a n i o n s t o g i v e
t e t r a h e d r a l s p e c i e s , the acceptor a b i l i t y
generally decreases
Al ^
Ga
^
I n w i t h the p o s i t i o n of T l u n c e r t a i n .
however n o t a b l e d i s t i n c t i o n s
to the reduced
ability
of h e a v i e r e l e m e n t s
from b o r o n .
There
These a r i s e
t o form m u l t i p l e bonds and
are
i n part
to the
t o have c o o r d i n a t e numbers e x c e e d i n g
due
ability
four.
-107Thaliium
( I I I ) c h l o r i d e i s s o f t e r than T l ( l ) c h l o r i d e ,
b e c a u s e o f t h e i n e r t p a i r of e l e c t r o n s i n t h e
The
by
presence
6S
of e l e c t r o n s i n these o r b i t a l s d e c r e a s e s
a s h i e l d i n g a f f e c t on
the o u t e r d e l e c t r o n s and
T1C1„ would be a b e t t e r m a t c h i n g p a r t n e r
3
orbitals.
softness
consequently
f o r S„N...
4 4
( d ) T e t r a s u l p h u r t e t r a n i t r i d e a d d u c t s of antimony n i o b i u m
and t a n t a l u m h a l i d e s
The
p e n t a h a l i d e s o f Sb, Nb
and
Ta
form a d d u c t s w i t h
donors,
s u c h a s oxygen, n i t r o g e n e x h i b i t i n g v a r i o u s s t a b h i o m e t r i e s
(e.g.
142
S b C l . S e O C l , N b C l g . POClg, NbF .2NH , T a F ^ C g H g N )
5
2
5
p e n t a c h l o r i d e h a s been more e x t e n s i v e l y s t u d i e d t h a n
pentahalides
of Sb, Nb
conform t o 1:1
and
Ta and
stochiometry.
I n the boron h a l i d e s e r i e s
i n d e g r e e of
the order;
apparently
the
SbCl,. w i t h p y r i d i n e y i e l d s
o f a c i d s t r e n g t h s toward p y r i d i n e :
variations
other
C o m p a r i s o n of t h e v a l u e s of
y
BBr
O
SbCl,..
o
the
t h e m a j o r i t y of i t s a d d u c t s
h e a t s o f r e a c t i o n o f B B r ^ , B C l ^ and
the order
Antimony
3
BC1
^
o
(as previously described),
bonding h a v e been u s e d t o e x p l a i n
t h e p e n t a h a l i d e s may
d i s t u r b a n c e t o t h e d e g r e e of
coordinate with
bonding p r e s e n t .
little
The p h y s i c a l
p r o p e r t i e s of t h e a d d u c t s of p e n t a h a l i d e s v a r y but t h e m a j o r i t y
142
a r e s o l i d s a t room t e m p e r a t u r e
.
Antimony p e n t a f l u o r i d e h a s some
u n u s u a l c h e m i c a l b e h a v i o u r ( e . g . i t d i s s o l v e s S, Se, Te and from t h e
144
s o l u t i o n s c r y s t a l l i n e s u b s t a n c e s s u c h a s ( S b F )„S may be i s o l a t e d )
,
138
Antimony p e n t a f l u o r i d e
( e l e c t r o n e g a t i v i t y v a l u e s , Sb=1.82, F=:4.1
),
-108-
a s would be e x p e c t e d b e c a u s e o f t h e h i g h
affinity
o f antimony
( i n SbF,.) f o r e l e c t r o n s , f u n c t i o n s a s a s t r o n g L e w i s
The
a c i d s t r e n g t h o f SbF,. ( w i t h r e s p e c t
with
that of sulphur
t o S^N^) c a n be compared
t r i o x i d e , s i n c e b o t h t h e a c i d s g i v e S^N^
a d d u c t s o f 1:2 (S^N^ L e w i s
one
acid.
a c i d s ) and 1:4 s t o c h i o m e t r y .
When
o f t h e n i t r o g e n atoms o f S^N^ i s i n v o l v e d i n t h e a d d u c t
formation,
t h e donor a b i l i t y
weakened, b u t i n t h e p r e s e n c e
donor s i t e s
coordinate
o f o t h e r N atoms i s c o n s i d e r a b l y
of strong acceptors,
the other
o f S^N^, though weak c a n be u s e d i n t h e f o r m a t i o n
bonds, a l t h o u g h a c c o r d i n g
t o HSAB p r i n c i p l e ,
of
such
bonds would be weaker t h a n t h e bonds formed from b e t t e r matched
partners.
The p e n t a f l u o r i d e s o f n i o b i u m and t a n t a l i u m
adducts with
v a r i o u s donor l i g a n d s
and
h e x a f l u o r i d e anions
and
tantalum
give
( e . g . NbFg.OBtg, TaF,..Se*£)
a r e known f o r t h e s e e l e m e n t s .
'{.'
Niobium
a l s o e x h i b i t a c o o r d i n a t i o n number g r e a t e r t h a n s i x .
A c o o r d i n a t i o n number o f s e v e n h a s been formed f o r n i o b i u m i n
4
( N b F _ ) ^ , w h e r e a s s p e c i e s up t o ( T a F )** and p o s s i b l y ( T a F )
7
8
9
138
exist i n solution
.
The a c c e p t o r s t r e n g t h o f SbF,., NbF,. and
TaF,. toward S N
4
s i n c e SbF
1:1
o
4
i s probably
i n the order,
g i v e s 1:4 and 1:2 a d d u c t s ,
( S N : metal f l u o r i d e ) adducts.
4
4
t o s e e w h e t h e r SbFg d i s p l a c e s N b F
S N . T a F j . to g i v e S N
4
4
4
4
5
SbF
5
}
NbF
T
a
&
F
5
»
|l
i'
JI
w h e r e a s Nb and Ta form
However i t would be i n t e r e s t i n g
o r TaF,. from S N .NbF,. o r
4
4
a d d u c t s o f SbF,., b e c a u s e i t i s n o t p o s s i b l e
-109-
t o w r i t e down any
u n i v e r s a l order of a c i d s t r e n g t h ( i t v a r i e s
135
w i t h the r e f e r e n c e donor)
is
observed
.
As noted
f o r oxygen, n i t r o g e n and
above, a d d u c t
s u l p h u r donors
w i t h t h e p e n t a c h l o r i d e s and bromides o f Nb
t h e s t o b h i o m e t r y o f 1:1
<CH > S> .
and
1:2
formation
and T a ,
exhibiting
( e . g . NbClg.2(CH ^N, T a C l g .
3
1 4 2
3
2
Tantalum
p e n t a i o d i d e and NbX
(X=C1, B r , I ) a r e r e a d i l y
5
138
reduced
by p y r i d i n e t o g i v e MX^py^ c o m p l e x e s
( e ) T e t r a s u l p h u r t e t r a n i t r i d e a d d u c t s of s e l e n i u m ( I V )
t e l l u r i u m ( I V ) and t u n g s t e n h a l i d e s and o x y h a l i d e s
The
h a l i d e s of s e l e n i u m
( I V ) and
more s t a b l e t h a n t h o s e o f s u l p h u r and
tellurium
(IV) are generally
they a l s o d i f f e r
i n showing
138
Lewis a c i d i t y
( e . g . t h e y form complex h a l i d e s s u c h a s
K(SeF ), K (SeCl ),
5
2
g
(CjS^Telg)) .
s
Selenium
tetrachloride
forms
a d d i t i o n compounds w i t h ammonia, SeC1^.4NH , e t h y l e n e d i a m i n e
3
145
S e C l ^ ( e n ) , SeC1^.2en, and w i t h many amines
adduct
S e C l . . p y i s not a n a l o g o u s
4
Z
0
acetonitrilej'acts
like a salt
.
to SeCl-
2-
The p y r i d i n e
since
in
O
of the c a t i o n
+
( S e C l ^ .py^) ,
this
138
ion probably
h a s a d i s t o r t e d o c t a h e d r a l s t r u c t u r e , l i k e t h e SeOClg.pyg
Tellurium tetrachloride also gives TeCl 4NH
4 <
adducts
3
of the type T e C l . p y , T e C l , 2 p y , T e C l
4
4
w i t h d r y ammonia and
4 >
POCl
3
h a v e been
145
obtained
.
Frpm HSAB p r i n c i p l e , S e C l
classified
as s o f t Lewis a c i d s , s i n c e the s o f t Lewis a c i d s g e n e r a l l y
4
and T e C l
4
may
be
have a c c e p t o r atoms l a r g e i n s i z e , o f low p o s i t i v e c h a r g e
and
-110-
c o n t a i n i n g unshared p a i r s of e l e c t r o n s
valency s h e l l .
considerations
(p or d e l e c t r o n s )
Thus i n S e C l ^ and T e C l ^ , from
(e.n.
i n their
electronegativity
138
v a l u e s f o r Se=2.48, 01=2.83, Te=2.01)
would e x p e c t r e l a t i v e l y s m a l l
one
p o s i t i v e c h a r g e on S e and Te atoms,
3
and
s i n c e they c o n t a i n unshared p a i r s of e l e c t r o n s
o r b i t a l s and a l s o t h e y a r e r e l a t i v e l y l a r g e
Se=1.7L§, Te=1.37A*) c o n s e q u e n t l y S e C l
4
i n sp d hybrid
i n s i z e (covalent
and T e C l
4
may form
radii,
stable
c o m p l e x e s w i t h s o f t b a s e s e . g . TeCl «py would p r o b a b l y be more
4
stable
t h a n TeCl„.P0Cl_ and r e l a t i v e l y l e s s s t a b l e t h a n S . N . . T e C l .
4
3
4 4
4
J
(however HSAB p r i n c i p l e i s a q u a l i t a t i v e r u l e b a s e d on e x p e r i m e n t a l
facts,
t h e above o r d e r may be d i s t u r b e d
S e l e n i u m t e t r a f l u o r i d e and t e l l u r i u m
by o t h e r f a c t o r s ) .
t e t r a f l u o r i d e a r e highly
r e a c t i v e f l u o r i n a t i n g a g e n t s though t e l l u r i u m
tetrafluoride
appears
t o be l e s s u s e f u l
as a f l u o r i n a t i n g agent.
I t forms 1:1 a d d i t i o n
145
compound w i t h p y r i d i n e i n d r y e t h e r
; the tetrafluoride reacts
e x o t h e r m i c a l l y w i t h a number o f b a s e s , b u t s e c o n d a r y r e a c t i o n s
146
o c c u r r e d b e f o r e t h e c o m p l e x e s c o u l d be i s o l a t e d i n p u r e form.
T u n g s t e n h e x a c h l o r i d e , WClg i s r e d u c e d by p r i m a r y amines
138
t o g i v e amido c o m p l e x e s i n l o w e r o x i d a t i o n
i n a n a l o g y t o t h e S.N„ r e a c t i o n s
4 4
reaction
and
of o x y t e t r a h a l i d e s
bidentate ligands
W0C1
states
, which i s
w i t h WC1_ and W B r „ .
6
o
4
and W 0 B r
4
The
with various
unidentate
c o n t a i n i n g group V and group V I donor atoms
147
has
been r e c e n t l y
ethers
studied
.
A l k y l cyanides, pyridine
g i v e 1:1 a d d u c t s and t h e a l k y l c y a n i d e c o m p l e x e s
and c y c l i c
(e.g.
-111-
W0C1 ,CH„CN, WOC1 ..C,H CN) a p p e a r t o be s i x - c o o r d i n a t e c o m p l e x e s .
The
i n f r a r e d s p e c t r a o f WC1..S.N., WBr..S.N. and W0C1..S.N
4 4
4
4 4 4
4 4 n
are d i s c u s s e d
The
later.
S t r u c t u r e s o f S.N. a d d u c t s
4 4
The p o s i t i o n s o f t h e i n f r a r e d a b s o r p t i o n s
adducts a r e given i n Table
bond by d o n a t i o n
donor m o l e c u l e ,
2.
The f o r m a t i o n
o f t h e S^N^
of a coordinate
o f a lone p a i r of e l e c t r o n s merely p e r t u r b s t h e
no g r e a t changes i n s t e r e o c h e m i s t r y
r e q u i r e d and t h e e f f e c t
a r e commonly
on t h e s p e c t r u m a p p e a r s a s s m a l l
shifts
137 142
i n frequency,
w i t h p e r h a p s s p i t t i n g o f bands and a l t e r e d
I n t h e c a s e o f S^N^ more marked c h a n g e s o c c u r .
change i n t h e geometry o f S^N^, l o w e r i n g
Even
intensity
without
of the molecular
symmetry on c o o r d i n a t i o n g i v e s r i s e t o more i n f r a r e d - a c t i v e
bands.
S i n c e c o o r d i n a t i o n by n i t r o g e n atoms f l a t t e n s o u t t h e S^N^
molecule with
l o s s o f S-S bonds and SN bond l e n g t h s no l o n g e r
e q u a l , f u r t h e r changes a r e i n e v i t a b l e .
As a d i a g n o s t i c t o o l
i n f r a r e d s p e c t r u m i s i n v a l u a b l e and t h e s p e c t r a o f c o o r d i n a t e d
l i g a n d s f r e q u e n t l y show c o n s i d e r a b l e s i m i l a r i t i e s
o f compounds.
Examination
i n a wide
variety
of t h e element-halogen v i b r a t i o n s
a s w e l l a s t h e l i g a n d v i b r a t i o n s would a p p e a r t o o f f e r a t o o l t o
i n v e s t i g a t e the stereochemistry of the adducts.
shown t h a t m e t a l - h a l o g e n a b s o r p t i o n
i n t e n s e , and t h e r e f o r e r e a d i l y
bands
R e c e n t s t u d i e s have
(MX) a r e o f t e n
i d e n t i f i a b l e and t h a t t h e f r e q u e n c i e s
'
,
-112-
TABLE 2
VIBRATIONAL FREQUENCIES OF S.N. ADDUCTS WITH
METAL HALIDES
* *
The f o l l o w i n g s y m b o l s a r e u s e d t o
of t h e i n f r a r e d
denote the r e l a t i v e
intensity
a b s o r p t i o n s : v s = v e r y s t r o n g , s = s t r o n g , m = medium,
w = weak, vw = v e r y weak, b r = b r o a d , s h = s h o u l d e r .
SnBr .2S N
4
4
4
1156 vw, 1041 v s , 961 v s , 794 v s , 725 vw, 671 ms,
621 m s ( B r ) , 563 w, 513 s , 422 v s , 355 v s , 298 ms,
259 w, 234 s , 219 ms ( B r ) cm
SnCl .2S N
4
4
4
1
.
1170 vw, 1047 v s , 966 v s , 814 v s , 787 w ( s h ) , 722 vw,
683 w, 623 ms, 568 vw, 516 s , 413 s , 365 v s , 319 v w ( s h ) ,
309 v s , 279 ms, 260 vw, 252 w, 245 v w ( s h ) , 236 s ,
225 w, 212 vw, 207 vw, 201 vw cm
TiBr .S N
4
4
\
1156 vw, 1036 v s , 936 v s , 929 v s , 807 s , 775 v s ,
4
746 ms ( s h ) , 681 ms, 621 w, 565 m s ( b r ) , 508 s , 416 w,
365 w, ( 3 2 2 w, 312 w, 299 w ) ( b r ) , 280 vw, 279 w, 266 w,
253 w, 245 ms, 226 w, 220 w, 217 vw, 212 w, 211 w ( s h ) ,
206 w cm *.
TiCl
.S N
fr
ft
1156 vw, 1041 w, 990 vw, 963 s , 927 v s , 810 w, 760 ms,
ft
728 s , 700 v s , 620 vw, 549 v s , 529 v w ( s h ) , 515 vw, 389
vw ( s h ) , 370 v s , 340 v s cm
TiF
Til
4
1
.
.S N
4 4
1149 vw, 1059 v s , 985 v s , 724 w ( s h ) , 662 v s ( b r ) ,
613 vw,
_^
510 ms, 510 vw, 378 ms, 351 vw, 282 s ( b r ) , 247 vw cm .
.S N
1156 vw, 1098 vw, 1020 w, 934 w, 793 w, 722 vw,
-1
279 s , 248 s ( b r ) cm
ZrCl .S N
4
4
4
.
1157 vw, 1034 v s , 957 v s , 807 v s , 795 v w ( s h ) , 762 v s ,
740 vw, 722 v s , 699 v s , 668 v w ( s h ) , 626 ms, 551 v s ,
529 vw, 510 ms, 367 w ( s h ) , 340 v s , 305 ms, 245 vw cm
HfCl .S N
4
4
4
\
1156 vw, 1037 v s , 991 vw, 958 v s , 800 v s , 724 v w ( s h ) ,
682 s , 666 vw, 639 v w ( s h ) , 624 s , 561 vw, 553vw, 514 v s ,
422 vw, 399 vw, 359 w ( s h ) , 324 s ( b r ) , 303 vw,
290 vw, 279 w, 267 w, 253 m s ( s h ) , 247 s , 226 w, 220 w,
217 vw, 212 w, 206 w.
-113-
TABLE 2 Ccnntd
1156 vw, 1058 v s , 975 v s , 807 v s , 786 v s , 738 w ( s h ) , 722 ms
SbCl .S N
5
4 4
c
/ 1
1
> 1
( b r ) , 682 s , 666 vw, 651 w, 623 v s , 608 v w ( s h ) , 563 w,
511 v s , 483 vw, 411 v s , 370 s ( s h ) , 370 w ( s h ) , 361 w ( s h ) ,
1
345 v s , 308 s , 275 v s , 245 s , 239 w ( s h ) , 226 w cm
4SbF .S N
5
4 4
.
1143 vw, 1058 v s , 986 v s , 943 v s , 886 v w ( s h ) , 790 ms, 741 ms,
c
719 v w ( s h ) , 695 s , 625 s , 571 s ( b r ) , 429 v s , 357 s , 339 s ( b r ) ,
291 ms, 268 vw, 259 w, 250 v w ( s h ) , 234 w, 228 w, 223 w,
214 w, 208 w cm
NbCl .S N
5
4
1
.
1041 v s , 987 ms, 954 v s , 883 ms, 788 v s , 750 s ,
4
719 vw, 680 ms, 666 vw, 618 s , 506 v s , 431 ms, 365 v s , 340 v s
-1
cm
NbF .S N
5
4
4
1065 v s , 992 v s , 929 w, 891 vw, 800 ms, 722 ms, 676 ms,
606 v s ( b r ) ,
TaCl .S N
5
4
515 v s .
4
1153 vw, 1045 v s , 957 v s , 797 v s , 749 s , 721 v w ( s h ) ,
682 ms, 669 vw, 637 m s ( s h ) , 619 s , 568 vw, 505 v s , 425 ms,
372 w ( s h ) , 359 m s ( s h ) ,
226 w cm
TaF .S N
5
4
1
322 v s ( b r ) , 265 w, 252 vw, 244 vw,
.
4
1153 vw, 1071 v s , 996 v s , 927 v s , 873 v w ( s h ) , 803 ms,
BF .S N
3
4
744 ms, 727 w, 700 v s , 678 ms, 667 vw, 581 v s ( b r ) ,
-1
.
516 w
cm
54
1171 w, 1138 ms, 1117 s , 1070 s , 1040 v s , 1014 w, 949 s ,
4
908 w, 888 s , 840 w, 724 vw, 697 vw, 682 vw, 658 ms, 623 ms,
567 w, 552 w, 527 s , 502 w, 490 w ( s h ) , 420 ms cm
BC1 .S N
3
4
1
.
54
1064 s , 1042 w, 982 s , 958 s , 864 w, 736 w, 720 w, 695 w,
4
678 w, 660 w, 625 w, 615 v w ( s h ) , 552 vw, 518 w, 430 w, cm
PhBCl .S N
2
4
4
1
.
1310 vw, 1156 v w ( s h ) , 1087 v w ( s h ) , 1265 vw, 1194 v w ( s h ) ,
1186 v w ( s h ) , 1174 v s , 1057 v s , 1029 w ( s h ) , 1000 v w ( s h ) ,
971 w ( s h ) , 948 v w ( s h ) , 921 v s , 888 w ( s h ) , 875 s , 857 v w ( s h ) ,
797 ms, 762 ms, 738 v w ( s h ) , 725 v w ( s h ) , 704 v s , 693 v w ( s h ) ,
659 v s , 628 ms, 615 v w ( s h ) , 551 s , 521 s , 420 v s , 359 v s ,
352 v w ( s h ) , 335 v s , 314 v s , 304 v w ( s h ) , 282 v s , 261 w, 250 v s ,
241 w, 238 v w ( s h ) , 233 v w ( s h ) , 228 ms, 222 w, 218 vw, 213 vw,
208
w.
-114-
TABLE 2 ( c o n t d . . . . )
2 A l B r . . S .N
3
4 4
1157
710
vw, 1126 v s , 934 ms, 869 v s , 776 ms, 736 ms,
v w ( s h ) , 694 vw, 667 w, 633 w, 585 ms, 565 w, 481 vw
(sh),
473 v s , 457 w, 437 ms, 414 ms, 395 ms, 349 v s ,
318 ms, 276 ms, 259 ms, 251 ms, 244 ms, 238 vw, 226 s ,
221 w ( s h ) , 212 ms, 206 ms cm
2A1C1 .S N
3
4
4
1162
1
.
vw, 1046 v s , 998 w, 967 v s , 866 v s , 800 vw,
755 ms, 719 w, 680 ms, 623 s , 573 w, 561 w, 530 w ( s h ) ,
507 v w ( b r ) , 476 w, 454 ms, 403 v s , 355 v s , 324 v s ,
238
2GaCl .S N
3
4
4
1147
s , 225 ms cm
3
4
4
.
vw, 1033 v s , 993 w, 961 v s , 844 v s , 756 ms,
722
v w ( s h ) , 680 ms, 666 v w ( s h ) , 680 ms, 623 s , 566 w,
516
v s , ( 4 2 0 s , 408 s , 389 s , 374 s ) ( B r ) ,
267 v s , 228 s cm
2InCl .S N
1
1266
1
297 v s ,
.
ms, 1152 vw, 1040 v s , 954 v s , 893 vw, 824 v s ,
777 m s ( s h ) , 730 v s , 704 ms, 681 s , 645 v w ( s h ) , 621 v s ,
2T1C1 .S N
3
4
4
565
ms, 551 v w ( s h ) , 521 v s , 403 v s , 361 v s , 312 v s ,
236
m s ( b r ) cm
1156
1
.
vw, 1059 v s , 971 v s , 803 w, 741 w ( s h ) , 722 s ,
702 w, 655 w, 619 ms, 597 s , 580 s , 558 w, 533 ms,
523 w cm
2FeCl .S N
3
4
4
1162
1
.
vw, 1033 v s , 995 w, 957 v s , 797 v s , 737 ms, 720
v w ( s h ) , 679 s , 619 v s , 565 w, 516 v s , ( 3 8 4 v s ,
370 v s ) ( b r ) ,
228
SeCl .S N
4
4
TeCl .S N
4
4
4
4
1190
vw cm
1
340 s , 308 s , 255 vw, 248 vw, 234 w,
.
w, 1124 v s , 1105 m s ( s h ) , 1016 ms, 945 w, 919 ms,
800
vw, 729 v s , 702 vw, 670 ms, 622 v s , 559
546
v s , 403 s , 383 s , 336 s , 309 s cm
1156
671
251
1
.
vw, 1047 v s , 966 v s , 806 s , 760 v s ,
ms, 635 ms, 613 ms, 563 w, 500 s ( b r ) ,
s(br),
225 w cm
1
.
s(sh),
727vw(sh),
360
vs(br),
-115TABLE 2 ( c o n t d . . . . )
TeF .S N
4
4
1282 w, 1162 vw, 1036 s , 981 v s , 926 v s , 926 v s ,
4
W0C1 .S N (?)
4
4
4
865
vw, 821 w, 768 s , 745 vw, 727 s , 700 v s , 627 vw,
591
vw, 458 v s cm ^.
1164 vw, 1075 vw, 1000 v w ( s h ) , 980 v s , 926 vw, 857 w,
837 w, 792 w, 778 w,
( 7 3 5 w, 723 w ) ( b r ) , 697 w, 662 v s ,
617 vw, 551 w, 543 w, 515 ms cm
WC1
.S N
\
1162 vw, 1119 w, 1070 vw, 1041 w ( s h ) , 1010 v s , 971 ms,
934 w, 851 ms, 800 v w ( s h ) , 788 v s , 768 w ( s h ) , 723 vw,
703
s , 697 v w ( s h ) , ( 6 6 0 s , 647 s ) ( b r ) ,
576 vw,
554 s , 515 v s , 494 m s ( s h ) , 4 7 2 vw, 406 ms, ( 3 5 0 w
(sh),
331 v s , 312 w, 294 w ( s h ) , ( b r ) ,
251 ms, 244 ms cm
WBr .S N
4
4
4
1169 w,
(br),
1
276 vw, 263 ms,
.
1066 vw, 1005 v s , 921 vw, ( 8 5 7 s , 837 s )
780 ms, 769 ms, 735 w ( s h ) , 722 w, 689 ms, 673 vw,
660
v w ( s h ) , 653 v s , 623 vw, 548 s , 527 ms, 514 ms,
501
v w ( s h ) , 467 s , 405 v s , 330 v s , 312 ms, 291 s ,
279
s , 263 ms, 254 w cm
1
.
-116o f t h e s e v i b r a t i o n s a r e r e l a t e d t o t h e o x i d a t i o n s t a t e and
c o o r d i n a t i o n number o f t h e m e t a l and a l s o t o t h e s t e r e o c h e m i s t r y
148
o f t h e complex
.
Thus a n i n c r e a s e i n c o o r d i n a t i o n number
149
i n v M-Cl
, e.g.
leads to a decrease
Sn
IV
IV
^~
( S n Cl„)
6
Cl,
4
v l = 368 cm"
1
311 c m "
1
149
and
an i n c r e a s e i n o x i d a t i o n s t a t e c a u s e s
2
e.g.
(FeCl ) ",
4
286 cm"
Also
(FeCl
1
377
)
_
a n i n c r e a s e i n v M-Cl
1
cm"
1
i n u s i n g v i b r a t i o n a l d a t a , one s h o u l d
be aware of t h e
importance of environmental e f f e c t s such a s f i e l d
e f f e c t s , and s i t e
.
symmetry e f f e c t s .
affects,
solvent
However, t h e s p e c t r a o f
s e v e r a l adducts c o n t a i n i n g supposedly c h e l a t e l i g a n d s , such as
i
1 , 1 0 - p h e n a n t h r o l i n e and 2,2 - b i p y r i d y l show t h a t t h e a s s i g n m e n t s
of s t e r e o c h e m i s t r y
c a n be made, i n t h e a b s e n c e o f
s-
f a c t o r s such
as c r y s t a l
is particularly
From T a b l e
N
w
^4 4 *
t
n
m
e
t
&
l
137
field effects
because i t i n v o l v e s the d i r e c t
study
.
h a l i d e s may
4
5
and S N . B F
4
4
3
i s u s e f u l t o compare t h e i n f r a r e d s p e c t r a o f t h e s e
with the other
complexes.
bond
stretching frequencies.
be d i v i d e d i n t o f o u r
Since the X-ray s t r u c t u r e s of S N . S b C l
it
spectroscopy
that the s p e c t r a of the adducts of
roughly
4
For i n f r a r e d
of t h e m e t a l - l i g a n d
u s e f u l i n a s s i g n i n g M-X
2 i t c a n be s e e n
complicating
types.
a r e known,
adducts
-117-
( a ) The a d d u c t s , S n B r . 2 S N
4
4
SnCl
4 >
2S N , TiBr .S N ,
4 #
4
4
4
4
ZrCl .S N
4
4
HfCl .S N , 4TiF .S N , 4SbF .S N , S b C l g . S ^ ,
NbCl^S^,
TaCl .S N , TaF .S N , T e C l ^ S ^ ,
2GaCl .S N ,
4
4
5
4
4
4
2InCl .S N
3
4
4
5
4 J
4
4
4
5
4
4
4
2A1C1 .S N ,
3
4
4
3
2 T 1 C 1 . S N ( ? ) have r o u g h l y s i m i l a r
3
4
4
s t r o n g peaks a t
4
1040,
4
960,
4 >
BF
3
510 and
4 >
4
infrared
4
s p e c t r a t o t h o s e o f S N . S b C l , . and S N
4
4
with
characteristic
360 cm
1
.
( b ) The i n f r a r e d s p e c t r a o f S.N..W0C1,,, S.N..WC1. and S.N^.WBr.
*
4 4
4
4 4 4
4 4 4
are d i f f e r e n t
from S N . S b C l
4
4
5
and S N . B F , b u t show s i m i l a r i t y
4
4
3
t o one a n o t h e r w i t h c h a r a c t e r i s t i c v e r y s t r o n g peak n e a r
The s t r o n g p e a k s
at
1040 and
1060
( c ) The
1
.
i n t h e above a d d u c t a r e
m i s s i n g i n thsfee a d d u c t s , t h e s t r o n g p e a k s
698 cm
1000 cm
inS N
4
a t 9 2 4 , 727 a n d
4
a r ealso missing i n these adducts.
i n f r a r e d s p e c t r a of 2 A l B r
3 <
S N
4
4
and S e C l
4 <
S N are
4
4
d i f f e r e n t from t h e above and one a n o t h e r .
( d ) The i n f r a r e d spectrum
of T i I » S N
4
4
4
i s weak.
The S t r u c t u r e s o f SnBr„.2S„N„ and SnCl„.2S.N„
4
4 4
4
4 4
The
based
s t r u c t u r e s t o be e x p e c t e d o f t h e s e a d d u c t s a r e t h a t
on a n o c t a h e d r a l d i s t r i b u t i o n about
A s i n g l e S n - C l band h a s been o b s e r v e d
t h e c e n t r a l metal
atom.
i n t i n ( I V ) c h l o r i d e complexes
151
with n i t r o g e n donors, such a s p y r i d i n e
324 cm
(e.g. SnCl .2py,
4
Sn-Cl,
b u t a p l i t t i n g o f t h i s band h a s been o b s e r v e d i n
complexes such a s S n C ^ . 2 , 2 ' - b i p y r i d y l
(
v S n - C l , 327, 280 cm
-1 151
)
-118-
From t h i s
i t was
concluded
t h a t the former c o m p l e x e s a r e
trans
151
o c t a h e d r a l , whereas the l a t t e r a r e c i s o c t a h e d r a l
i n f r a r e d spectra of S n C l . 2 S N
4
r e g i o n a r e very
and
4
4
4
a t 986 cm
1
4
.
direct
4
The
i n 400-4000 cm
i d e n t i c a l except
structures.
i s of p a r t i c u l a r
1
that i n
1
cm
to
has
conclude
The
metal-
interest since
i n f o r m a t i o n about t h e c o o r d i n a t e
Because of the r e l a t i v e l y
bond o r d e r
4
Hence i t i s r e a s o n a b l e
n i t r o g e n s t r e t c h i n g frequency
provides
4
t h e v e r y s t r o n g peak a t 813
t h a t both the adducts have s i m i l a r
it
SnBr .2S N
s i m i l a r or v i r t u a l l y
the case of S n C l . 2 S N
a shoulder
4
.
bond.
heavy mass of t h e m e t a l and
low
of the c o o r d i n a t e
bond, t h e M-N s t r e t c h i n g v i b r a t i o n s
156
may a p p e a r i n t h e low f r e q u e n c y r e g i o n
.
The a s s i g n m e n t
o f m e t a l - n i t r o g e n s t r e t c h i n g f r e q u e n c y i s c a r r i e d out by
c a l c u l a t i n g approximate metal n i t r o g e n f o r c e constant
from
157
Gordys r u l e
and
then c a l c u l a t i n g the approximate
stretching
frequency.
metal-nitrogen
159
T h i s method i s s i m i l a r t o t h e method d e s c r i b e d by
f o r c a l c u l a t i n g Sn-0
s t r e t c h i n g frequency
v a l u e of f o r c e c o n s t a n t , except
from t h e
Poller
approximate
t h a t the metal-nitrogen
bond
l e n g t h s u s e d were from t h e X - r a y d a t a o f t h e a d d u c t o f S N
o 58
with S b C l
(Sb-N=2.17A)
w h e r e a s P o l l e r c a l c u l a t e d t h e Sn-0
o
bond l e n g t h from t h e sum of t h e c o v a l e n t r a d i i c o r r e c t e d f o r
160
4
4
c
the e l c t r o n e g a t i v i t y
of S n C l . 2 S N
4
4
4
and
difference
SnBr
4 >
2S N
4
4
.
S i n c e the i n f r a r e d
are very s i m i l a r
to the
spectra
infrared
-119-
s p e c t r u m of S.N
stretching
Sn-N
.SbCl
frequency
, i t i s u s e f u l to a s s i g n the
first
i n S ^ N ^ . S b C l ^ and
stretching frequencies in SnCl .2S N
4
comparison.
4
4
metal-nitrogen
then a s s i g n the
and
SnBr .2S N
4
4
by
4
Thus t a k i n g e l e c t r o n e g a t i v i t y v a l u e s of 3.07
for
138
nitrogen
(Allred-Rochow s c a l e )
Rochow s c a l e )
and
t h e N-Sb
and
1.82
f o r antimony
bond l e n g t h of 2.
a
(Allred-
force
5
constant
o f 2.2
x 10
dyn./cm. WAS o b t a i n e d
T h i s gave a v a l u e of 545
If
cm
1
f o r t h e N-Sb
( s e e Appendix
s t r e t c h i n g frequency.
t h e e l e c t r o n e g a t i v i t y v a l u e s f o r n i t r o g e n and
138
3.04
and
2.05
(Pauling-type values)
gave a s t r e t c h i n g f r e q u e n c y
are probably
upper l i m i t s
( h a l o g e n s ) atoms a t t a c h e d
of the
cm
a p p r o x i m a t i o n , one
s t r e t c h i n g f r e q u e n c i e s near
(atomic
.
I f such
These
weights,
other
types
and
Sn=118.69, Sb=121.80, E.N.
of
may
t h e above v a l u e s .
antimony a r e of c o m p a r a b l e a t o m i c w e i g h t s
ativities
1
the
l a r g e mass of t h e
t o t h e m e t a l atom.
c a l c u l a t i o n s a r e c o r r e c t as a f i r s t
t i n and
o f 565
are
to the a n t i c i p a t e d m e t a l - n i t r o g e n
s t r e t c h i n g f r e q u e n c y , on a c c o u n t
a s s i g n N-Sb
antimony
respectively,
calculations
1)
Since
electronegvalues,
138
Sn=1.96, Sb=2.04)
and
(Sn=1.4oX, Sb=l ,4lS)''"^^it
b o t h h a v e n e a r l y t h e same c o v a l e n t
i s reasonable
to expect
the
radii
Sn-N
s t r e t c h i n g f r e q u e n c i e s i n the r e g i o n of
Sn-N.
The m e t a l - c h l o r i n e v i b r a t i o n a l f r e q u e n c i e s l i e i n t h e b r o a d
149
-1
range
650-200 cm
and t h e o c t a h e d r a l S n ( I V ) c o m p l e x e s show
no
S n - C l a b s o r p t i o n s above 400 cm \
T h e r e f o r e a l l t h e bands
-120-
above 700 cm
1
i n t h e s e a d d u c t s a r e a s s i g n e d t o S-N v i b r a t i o n s .
Thus t h e v e r y s t r o n g bands a t
assigned to
1040,
940 and
S-N ( n o S n - h a l o g e n o r Sn-N bands a r e t o be e x p e c t e d
i n t h i s r e g i o n , b e c a u s e o f t h e above l i m i t s
halogen f r e q u e n c i e s ) , i n these adducts.
at
515 and
N
^4 4
n
a
s
a
r
800 a r e
360 cm
1
are assigned
The v e r y s t r o n g bands
t o S-N v i b r a t i o n s , b e c a u s e
n
1
*- £ s t r e t c h i n g mode a t 531 cm
mode a t 347 cm
1
- l
6
f o r Sn-N and S n -
and a r i n g
1
.
The v e r y
deformation
-1
410 cm
i n these
s t r o n g band a t
a d d u c t s may be ( 1 ) from t h e S-N r i n g s y s t e m , a s t h e l o w e r i n g
o f symmetry o f S^N^ g i v e s r i s e t o a d d i t i o n a l bands, o r ( 2 )
Sn-N
1
(SnCl .2S N
4
4
4
= 413 cm" , S n B r . 2 S N
4
4
1
= 420 c m " ) .
4
S e v e r a l p a p e r s have a p p e a r e d i n t h e p a s t few y e a r s d e a l i n g w i t h
t h e low f r e q u e n c y
tetrachloride
over
150,
s p e c t r a o f some n i t r i l e a d d u c t s o f t i n
151, 152, 153, 154
.
_
T h e r e h a s been
ml
t h e a s s i g n m e n t o f t h e bands below 500 cm
1
controversy
i n t h e spectrum
153
of S n C l
,2CH CN.
Brown and K u b o t a
bands a r o u n d 400 cm
1
originally
assigned the
a s S n - C l s t r e t c h i n g modes, w h e r e a s
bands o c c u r r i n g between 350 and 300 cm
1
those
were a s s i g n e d t o t h e
151
a s s y m e t r i c and s y m m e t r i c Sn-N v i b r a t i o n s .
Beattie
et al.,
however, showed t h a t t h e a s s i g n m e n t s o f Brown and Kubota were
incorrect;
they
a s s i g n e d t h e bands around 400 cm ^ a s l i g a n d
vibrations
(NCC b e n d i n g modes) and lower
stretching vibrations.
frequency
bands a s S n - C l
On t h e b a s i s o f s i m p l e v a l e n c y f o r c e f i e l d
155
c a l c u l a t i o n s , B e a t t i e and R u l e
p r e d i c t e d t h a t t h e Sn-N s t r e t c h i n g
-121frequency
f o r SnCl^.aCHgUN would o c c u r
A g g a r w a l and
Singh
o f some amide, u r e a and
below 265
on t h e b a s i s o f t h e low
cm
\
frequency
spectra
a m i n o b e n z o i c a c i d a d d u c t s of t i n t e t r a -
c h l o r i d e , r e v e r s e d t h e a s s i g n m e n t of B e a t t i e e t a l . ,
and
support
153
those
of Brown and
Kubota
.
They o b s e r v e d
a s t r o n g band
i n t i n ( I V ) c h l o r i d e , / ? c o m p l e x e s w i t h n i t r o g e n donors a t about
310
cm
^, but ho band i s p r e s e n t
i n t h i s r e g i o n i n the t i n ( I V )
c h l o r i d e c o m p l e x e s w i t h oxygen d o n o r s ; had
to a Sn-Cl v i b r a t i o n , then
i t should
t h i s band been
due
have a p p e a r e d i n a l l t h e
c o m p l e x e s of t i n ( I V ) c h l o r i d e w i t h n i t r o g e n a s w e l l a s oxygen
donors.
150
However, F o w l e s
e t . a l . , and
t h e a s s i g n m e n t of B e a t t i e e t a l .
i n t h e 300
adducts,
- 370 cm
4
They a s s i g n e d t h e bands
i n the s p e c t r a of corresponding
4
appearing
SnCl^
SnBr^
and
a t 319
cm
1
.
S i n c e t h i s band i s m i s s i n g
i n the i n f r a r e d spectrum of S n B r . 2 S N
4
a s s i g n t h e band a t 308
medium s t r o n g bands a t
s p e c t r a of S n C l . 2 S N
4
1
t h e r e i s a v e r y s t r o n g b r o a d band a t 308 cm
4
w i t h a v e r y weak s h o u l d e r
4
4
cm
4
4 >
i t i s reasonable
to
* to Sn-Cl s t r e t c h i n g v i b r a t i o n .
235
and
cm
^ which appear i n both the
SnBr .2S N , are assigned
4
medium s t r o n g b r o a d band a t 219
assigned
e t a l . , support
t o S n - C l s t r e t c h i n g modes.
In S n C l . 2 S N
The
152
^ r e g i o n , i n t h e s p e c t r a of a l l t h e
but m i s s i n g
S n l ^ adducts,
Farona
4
to
4
cm
1
in SnBr .2S N
4
4
4
The
infrared
Sn-N.
is
t o Sn-Br v i b r a t i o n , s i n c e a medium s t r o n g band a t 220
cm
^
-122-
has
been a s s i g n e d t o S n - o r mode i n t h e adducL S H B I ^ . 2 , 2 - b i p y r i d y l
I t was
in
found t o be
difficult
t o a s s i g n t h e o t h e r bands
t h e i n f r a r e d s p e c t r a o f S n C l . .2S.N. and
4
4 4
151
Beattie et a l . ,
frequency
and
( 3 2 4 cm
1
have
observed
) i n the f a r i n f r a r e d
predicted a trans structure
b i p y r i d y l two
S n - C l and
usually
one
S^N^ i s a l s o a s t e r i c a l l y h i n d e r e d
SnC1..2S„N. and SnBr..2S.N. may be
4
4 4
4
4 4
J
w h i c h w e r e found t o be d i f f i c u l t
4
proposed.
hindered
4
l i g a n d , the s t r u c t u r e s of
trans octahedral.
However
s p e c t r a of t h e s e
t o a s s i g n and
some o f
t o be
4
4
4
4
adducts,
these
t o S n - C l v i b r a t i o n s , w h i c h would t h e n
t r a n s appears
as
therefore since
favour
Thus t h e c h o i c e
difficult.
S t r u c t u r e s of S N . 4 T i F , S N « T i B r , S N . T i F
4
Because
l i g a n d s ) such
a c i s octahedral s t r u c t u r e for these adducts.
S N .HfCl
4
s , b r ) were a s s i g n e d t o
t h e r e a r e o t h e r bands i n t h e f a r i n f r a r e d
The
SnCl .2py
4
ligands (or s t e r i c a l l y
between c i s and
of
f o r SnCl »2py whereas i n S n C l . 2 , 2 ' -
bands (327 v s , b r , 280
be due
stretching
spectrum
pyridine give trans octahedral structure,
bands may
appearing
S n B r . , 2 S .N„.
4
4 4
Sn-Cl
a c i s o c t a h e d r a l s t r u c t u r e , was
large
152
4
4
4
4
4 >
S N .ZrCl
4
4
and
4
4 j
Titanium,
z i r c o n i u m and
hafnium h a l i d e s
form a w i d e
variety
170
of adducts
nitriles
o r 2:1
but
148
w i t h many oxygen and
, and
amides
171
.
(base:acid) adducts,
f o r m e r may
be e i t h e r
n i t r o g e n d o n o r s , e.g.
ethers
,
T h e s e compounds a r e u s u a l l y e i t h e r
the l a t t e r
1:1
a r e s i x c o o r d i n a t e monomers,
f i v e c o o r d i n a t e monomers, o r s i x c o o r d i n a t e
.
-123-
d i m e r s a s i n t h e compound ( T i C l
coordination
for titanium
has
.P0C1
)
Eight-
been e s t a b l i s h e d
for
bidentate
163
a r s i n e complexes of
The
and
titanium
(IV) halides
.
s t r u c t u r e s of S.N . . T i B r ., S.N„.TiF„, S . N - . Z r C l ^
4 4
4'
4 4
4'
4 4
4
S^N^.HfCl^, a d d u c t s a r e e x p e c t e d t o c o n t a i n
S^N^, s i n c e t h e i r s p e c t r a a r e s i m i l a r t o t h e
of S N
fx
.SbCl
ft
( m a j o r p e a k s a t , 1058,
S^^.BFg
( m a j o r p e a k s a t 1040,
one
nitrogen
o f S^N^ i s
ft
963,
508,
.ZrCl
4
360
365
, 1034,
1
cm" ;
957,
949,
1
957,
.
510,
368;
4
4
370
1
cm
4
502
S N
.HfCl
ft
)
4
4
4
1
) i n which only
The
corresponding
S^^.TiBr^,
510
, 1037,
958,
351
1
cm" ;
515,
fx
infrared spectra
of Z r C l ,
4
HfCl ,
4
i n f r a r e d spectrum
i n a number of r e s p e c t s , w h i l e
spectrum of H f C l . S N
cm
4
ft
However, t h e
S N .SbCl,_
|
spectra
S N . 4 T i F , 1059, 985,
4 T i F . , S.N. a r e d i f f e r e n t from t h e
4'
4 4
4
and
adducts occur a t
ft
cm
511
used i n c o o r d i n a t i o n .
c h a r a c t e r i s t i c p e a k s f o r t h e new
S N
infrared
<D
and
1036,
976,
unidentate
i s most l i k e t h e
the
of
infrared
i n f r a r e d spectrum
of
I
S N .SbClg.
4
4
Absorption frequencies
s i m i l a r i t i e s and
a d d u c t s and
S N .SbCl :
4
4
5
differences
i n the
and
the
outstanding
i n f r a r e d s p e c t r a of
S.N..SbCl,_ a r e g i v e n below:
4 4
o
1058
511
v s , 976
v s , 808
v s , 786
v s , 722
1037
v s , 958
v s , 800
v s , 741
s , 682
S N .ZrCl :
1034
v s , 957
v s , 807
v s , 762
v s , 722
4
4
4
4
4
551
ms, 682
s , 623
vs,
vs.
S N .HfCl :
4
these
v s , 510
ms
cm
\
s , 624
s , 415
v s , 699
vs
v s , 626
1
cm" .
ms,
-124-
S N .TiBr :
4
4
1037, 963 v s , 829 v s , 807 s , 746 ms, 681 ms,
4
1
621 w, 565 ms, 508 cm
S.N , 4 T i F
ft
fr
•.
1059 v s , 985 v s , 725 w, 662 v s ( b r ) ,
M-X f r e q u e n c i e s i n t h e above m e t a l h a l i d e s
r a n g e 650-200 cm
-1
(with exception of T i F
l i e i n t h e broad
172
h i g h e s t , T i - F = 880 w ( v . b r )
4
t h e s t r o n g bands above 700 cm * ( e x c e p t i n 4 T i F . S N > a r e
4
likely
at
510 ms,
ft
Since
all
.
t o be S-N s t r e t c h i n g f r e q u e n c i e s .
510 and
since S N
4
4
T h e common bands
365 cm ^ i n t h e s e a d d u c t s a r e a s s i g n e d
to
h a s a bond s t r e t c h i n g mode a t 545 and a bond
4
mode a t 347 cm
1
4
1
c a n be a s s i g n e d t o e i t h e r
wi t h o t h e r S N
4
in t h i s region
4
bending
4
t h e band
4
VS-N o r
V T i - N , by a n a l o g y
a d d u c t s , i n w h i c h M-N f r e q u e n c i e s a r e a s s i g n e d
(e.g. SnCl .2S N ,
4
4
4
1
Sn-N=413 cm
).
T h e r e a r e a number o f o t h e r p e a k s i n t h e f a r i n f r a r e d
o f T i B r » S N , w h i c h c a n n o t be a s s i g n e d w i t h
4
4
S-N,
respectively.
I n t h e f a r I n f r a r e d spectrum of T i B r . S N ,
a t 416 cm
4
spectrum
certainty.
4
I n t h e f a r i n f r a r e d spectrum of Z r C l . S N , t h e peaks a t
4
340 v s ( b r ) 304 ms cm
1
a r e assigned
frequencies are assigned
4
4
to v Z r - C l , since
i n t h e r e g i o n 299-354 cm
1
v Zr-Cl
i n the addition
148
compounds o f Z r C l
4
.
The i n f r a r e d s p e c t r u m o f S N
4
4 >
4TiF
4
h a s two p e a k s a t 1059 and 985 w h i c h a r e a s s i g n e d t o S-N s t r e t c h i n g
vibrations.
T h i s i n f r a r e d spectrum d i f f e r s
from t h e i n f r a r e d
s p e c t r u m o f S ^ N ^ S b C l , . i n t h a t t h e r e i s no v e r y
1
800 cm .
T h i s may be b e c a u s e i n T i F
4
s t r o n g peak a t
the highest metal-
•125-
1
f l u o r i n e frequency
f o r T i F ^ a t 880 cm
t h e S-N s t r e t c h i n g
f r e q u e n c i e s i n t h i s r e g i o n ; a l l t h e peaks
i n t h i s region a r e prohably
Ti-F
vibrations.
may c o u p l e
with
due t o t h e c o m b i n a t i o n o f S-N and
T h e r e i s b r o a d v e r y s t r o n g band a t 662 cm
w h i c h may be a s s i g n e d t o T i - F v i b r a t i o n s ,
f r e q u e n c i e s h a v e been a s s i g n e d
since Ti-F
stretching
i n t h e r e g i o n 550-670 cm ^ i n
167
T i F . 2 , 2 ' b n . p y r i d y l , TiF »2py
4
may
.
4
a l s o occur
absorptions
i n this
However T i - N
r e g i o n , and i t seems l i k e l y
t h a n s i m p l e group
I n t h e f a r i n f r a r e d s p e c t r u m o f S.N , 4 T i F
ft
ft
172
absorptions.
t h e band a t 283 ( v s , b r )
ft
i s a s s i g n e d t o T i - F bending v i b r a t i o n ,
of T i F ^
that the
i n t h e r e g i o n 728-615 may be due t o c o m b i n a t i o n o f
S-N, T i - N and T i - F modes r a t h e r
i s assigned
vibrations
to T i - F bending v i b r a t i o n
s i n c e a mode a t 280 s ( b r )
i n the infrared
spectrum
and a l s o b e c a u s e T i - F d e f o r m a t i o n s o c c u r a t 254-311 cm
-1
167
i n T i F ^ complexes
due
.
The medium s t r o n g band a t 370 c o u l d be
t o v S-N or. v T i - N .
In t h e i n f r a r e d spectrum of S N
4
b r o a d band a t 325 cm
1
4 <
HfCl
4
1
( s h o u l d e r a t 303 cm )
Hf-Cl vibration,
by a n a l o g y w i t h o t h e r S N
halides
4
The
4
(e.g. S N . Z r C l ,
4
4
Z r - C l 340, 305 cm
i n f r a r e d spectrum of T i I . . S N
4
m u l l s were s t r o n g ; t h e r e a s o n
reduced p o l a r i t y
forthis
4
4
strong
i sassigned to
adducts of metal
1
.
i s weak e v e n though t h e
i s p r e s u m a b l y due t o
o f bonds compared w i t h
the other t i t a n i u m h a l i d e s .
4
t h e very
the S N
4
4
complexes o f
I n t h e f a r i n f r a r e d spectrum o f t h i s
-126-
t h e r e i s a s t r o n g band a t 279 cm
Ti-I,
1
w h i c h c a n be a s s i g n e d t o
b e c a u s e m e t a l - i o d i n e bands u s u a l l y
frequencies.
occur a t lower
The commonly o c c u r r i n g bands a t
245 cm
i n a l l the t i t a n i u m h a l i d e s adducts a r e a s s i g n e d to
'
1
Ti-N
1
( i n Z r C l . S N , Zr-N=245 c m " ) .
4
4
4
None o f t h e above a d d u c t s o f S.N. w i t h T i B r . , TiCl„.
4 4
4
4
T i F , ZrCl^
4
and H f C l
4
has a sharp m e l t i n g p o i n t , i n f a c t
f o r the
most p a r t t h e y do not m e l t below 250°C a l t h o u g h most o f them
show s i g n s o f d e c o m p o s i t i o n below t h i s t e m p e r a t u r e .
complexes
whereas
have very l i t t l e
solubility
i n inert
solvents,
s o l v e n t s l i k e w a t e r , a l c o h o l s decompose t h e s e a d d u c t s .
These p r o p e r t i e s of the adducts probably i n d i c a t e
they may
These
that
not be p e n t a c o v a l e n t s u b s t a n c e s but r a t h e r t h a t
a r e p o l y m e r i c complexes,
a t l e a s t some of t h e s e complexes
they
may
be p o l y m e r i c .
The s t r u c t u r e s o f S . N . . S b C l , S.N..4SbF , S.N..NbCl , S.N..NbF_
4 4
5
4 4
5' 4 4
5'
4 4
5
S , N ^ . T a C l and S^N^.TaF
4 4
5
4 4
5
c
c
c
c
c
As a l r e a d y mentioned,
the X-ray s t r u c t u r e of S N .SbCl,.
4
i s known i n w h i c h S N. a c t s a s monodentate l i g a n d .
4 4
adducts of S N
4
4
4
A l l t h e above
w i t h t h e p e n t a h a l i d e s o f Sb,Nb and Ta may
have
s i x c o o r d i n a t e s t r u c t u r e s s i n c e the i n f r a r e d s p e c t r a of these adducts
a r e s i m i l a r to the i n f r a r e d spectrum of S N . S b C l g .
Absorption
f r e q u e n c i e s showing
differences,
4
4
t h e o u t s t a n d i n g s i m i l a r i t i e s and
i n t h e i n f r a r e d s p e c t r a o f t h e s e a d d u c t s a r e g i v e n below:
-1271
i-i
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m
CO
m
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m
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V)
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co
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i
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in
CM
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m
m
co
i-i
m
in
in
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>
i-i
in
10
(A
>
>
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CO
CM
CO
CO
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CO
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in
6
10
B
CM
co
CO
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GO
CO
CM
00
co
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CO
in
CM
CM
t>
m
t>
cn
10
10
W
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CO
00
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oo
oo
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r05
r-
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en
E
(0
E
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i-i
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o
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H
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25
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25
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25
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co
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cn
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m
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t>
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O
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o
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m
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•
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25
CO
i-H
25
25
1
W
o
iH
in
o
CCS
EH
•
25
25
co
CO
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CD
a
c
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<
-128-
I n S^N^SbCl,. t h e v e r y s t r o n g bands above 700 cm
4 4
5
assigned to
S-N ( h i g h e s t
= 395 cm ^ * ^ ) .
Sb-N = 565 cm
1
±
are
( c a ) , highest
Sb-Cl
The v e r y s t r o n g band a t 511 cm ^ i s a s s i g n e d
t o S-N v i b r a t i o n ,
because S N
fx
h a s a S-N r i n g s t r e t c h i n g mode
f t
a t 545 cm ^.
I n t h e f a r i n f r a r e d s p e c t r u m o f S.N. .SbCl_
4
band a t 411 cm
1
the strong
O
i s e i t h e r due t o S-N o r Sb-N v i b r a t i o n .
s t r o n g band a t 311 cm
a r i n g deformation
band a t 370 cm
4
1
1
i s assigned as
S-N, b e c a u s e S^N^ h a s
mode i n t h i s r e g i o n ( 3 4 7 cm
i s assigned
to
The
1
).
Sb-Cl s i n c e S b C l
The s t r o n g
has Sb-Cl
c
o
a b s o r p t i o n modes i n t h i s r e g i o n (
S b - C l = 395, 371 cm
1
1
in SbCl. ^)
0
However, t h e bands i n t h i s r e g i o n may a r i s e due t o t h e c o u p l i n g
o f S-N and S b - C l modes.
The v e r y s t r o n g broad band a t 345 cm
i n S^N^.SbClj. i s a s s i g n e d t o
adducts,
e.g. S N . 2 S n C l ,
4
4
4
S b - C l , by a n a l o g y
of S N
.SbCl,. c a n n o t
4
is
may
likely
that
i n the f a r infrared
be a s s i g n e d w i t h c e r t a i n t y .
spectrum
However, i t
in S N .SbClg are d i f f i c u l t
1
n i t r o g e n bonds.
The i n f r a r e d a c t i v e bands a p p e a r i n g
bands r a t h e r
.
s i n c e t h e p o l a r i t y of the metal-
h a l o g e n bonds i s h i g h e r t h a n t h e m e t a l
4
1
t h e r e l a t i v e l y weak bands a t 308 and 345 cm
be due t o Sb-N v i b r a t i o n s ,
4
w i t h o t h e r S^N^
S n - C l = 310 v b r ( s h . 3 1 9 ) cm
The number o f o t h e r bands a p p e a r i n g
1
to assign,
i n t h e r e g i o n 700-550 cm
since
t h a n s i m p l e group a b s o r p t i o n s .
t h e y may be
1
combination
-129-
I n S4^4'NbCig and S^N^.TaCl^ t h e s t r o n g
700 cm
1
v
a r e a s s i g n e d tm
S-N
by a n a l o g y w i t h
-1
(highest
1
in S N
.NbCl
w h e r e a s t h e band a t 363 cm
S.N..SbCl_.
Similarly
band a t 322 cm
360 cm
1
may
1
1
).
The
strong
i s assigned t o v Nb-Cl,
i s assigned t o
in S N
.TaCl
i s assigned
be due t o
S^N^.SbCl^
156.
v N b - C l i n N b C l g i s a t 497 cm
b a n d a t 340 cm
ban
S-N
analogy
the very strong
broad
T a - C l w h e r e a s t h e band a t
vS-N.
In a series of related molecules, v a r i a t i o n of metalh a l o g e n s t r e t c h i n g f r e q u e n c y w i t h m e t a l may
factors.
However,
i t i s a t l e a s t reasonable t o expect
a n i n c r e a s e i n mass o f t h e m e t a l w i l l
(M= m e t a l ,
4
M-X
4
4
4
S N .TaCl
5
4
340
M-X
4
5
322
)
In S N .4SbF , S N .NbF
4
cause a decrease i n ^
S N .NbCl
5
345
1
that
X=halogen).
S N .SbCl
(cm
depend u p o n s e v e r a l
4
a b o v e 800 cm
5
1
4
4
and S N . T a F
5
4
are assigned t o
606 v s ( b r ) , S N..TaF
1
M-F
mode o n l y s i n c e M-F
lie
i n this region
Ta-F
= 560 c m - 1 ) .
S-N
Sb-F
= 716 cm
(S N .4SbF =627 v s ( b r ) ,
4
4
5
\
a n d Sb-N
stretching
( e . g . NbF
g
bands
there i s a very strong
= 5 8 1 v s ( b r ) cm
t o t h e c o m b i n a t i o n o f M-F,
1 4 8
cm
the strong
5
vS-N ( h i g h e s t
In a l l these p e n t a f l u o r i d e adducts
b a n d i n t h e r e g i o n 666-526
4
,
w h i c h may
''^).
broad
S N
4
4 <
NbF =
5
be e i t h e r
modes o r may
1
due
be due t o
f r e q u e n c i e s i n o c t a h e d r a l complexes
Nb-F
= 585 cm
1
, TaF
g
,
-130-
The
Structures of S N
4
2A1C1 , S N .2AlBr
4 <
3
S N .2T1C1 , S N .2FeCl
4
4
3
The
4
infrared
of S N .2AlBr
4
4
spectrum
4
4
4
4
4
4
2
are s i m i l a r
the exception
t o the
i n t h e near
s p e c t r a o f t h e s e c o m p l e x e s c a n be done i n e x a c t l y
are described
The f a r i n f r a r e d
infrared
t h e same way
spectra o f a l l these
4
3
t h e s t r o n g b a n d a t 403 i s a s s i g n e d t o e i t h e r
S-N o r A l - N , w h e r e a s t h e b a n d a t 354 i s a s s i g n e d t o
by a n a l o g y
with other S N
4
i s assigned
adducts
4
adducts.
appear i n t h i s
Al-N
region.
vibration since this
1
4
frequencies i n S N
3
4
4
i n t h i s r e g i o n ( h i g h background
o f a b s o r p t i o n maximum)
4
The r e l a t i v e l y
S N . 2 G a C l , a t 228 c m " , S N . 2 I n C l
S-N
The v e r y s t r o n g b a n d a t 324
A l - C l , since metal-halogen
i s assigned t o
4
adducts
below.
In S N .2A1C1
4
with
f MCI
N
frequency assignments
as f o r S.N-.SbCl,..
4 4
o
infrared
S
N
infrared
4
below,
S
The
4
They a l l may h a v e s t r u c t u r e s
4
m o n o d e n t a t e S.N. a s shown
C1_M
S N .2GaCl , S N . 2 I n C l
3 >
spectra o f these adducts, w i t h
and S N .PhBCl
3
4
and S ^ . P h B C ^
3
o f S N .SbCl,..
4
4
3
4
weak b a n d a t 225 cm
band a l s o a p p e a r s i n
and S N . 2 F e C l
4
4
3
also
o f spectrum prevents exact
absorb
location
3
-131-
I n S N ,2GaCl_, t h e b a n d s i n t h e b r o a d e n v e l o p e a t 4 2 0 ,
4 0 8 , 389 a n d 374 cm
1
a r e p r o b a b l y due t o Ga-Cl a n d S-N
c o m b i n a t i o n modes, s i n c e g a l l i u m t r i c h l o r i d e
s t r o n g Ga-Cl bands i n t h i s r e g i o n 340-400 cm
•
•
i
348 - 2 a n d v asym ( G a - C l ) = 383 - 3 cm
b a n d s a t 297 a n d 267 a r e a s s i g n e d
the
relatively
w h e r e a s t h e b a n d a t 314 cm
1
to
403 may be due t o e i t h e r
1
384 a n d 370 cm
v In-Cl.
= 385 cm
1
5
~'' ^).
4
3
soluble i n inert
The s t r o n g
1
4
a t 308 cm
adducts.
S N .2GaCl , S N . 2 I n C l , S N .2T1C1
4
i s a s s i g n e d t o v S-N,
S-N = 354 cm ,
The b a n d
4
3
band
peaks
4
4
organic solvents
3
1
Fe-Cl i n
i s assigned t o
The a d d u c t s S N . 2 A 1 C 1
4
and S N . 2 F e C l
4
4
3
( e . g . CHgClg) i n d i c a t i n g
structures
+
4
2
S^^PhBClgi
4
f e w a s s i g n m e n t s c a n be made o n a c c o u n t o f
l a r g e number o f a d d i t i o n a l b a n d s d u e t o t h e p h e n y l
However t h e f a r i n f r a r e d
s i m p l e and s i m i l a r
group I I I h a l i d e s
group.
spectrum o f t h e adduct i s r e l a t i v e l y
i n many r e s p e c t s t o o t h e r S N
4
(e.g. S N .2A1C1 ).
4
4
3
4
3
that
t h e t y p e (S N . M X ) M X ~ .
For
the
4
are a l l
they probably are covalent s t r u c t u r e s rather than i o n i c
of
strong
i s p r o b a b l y a c o m b i n a t i o n band d u e t o t h e
Fe-Cl analogy w i t h o t h e r S N
4
The v e r y
s t r o n g band ( b r o a d ) w i t h
c o u p l i n g o f S-N a n d F e - C l modes (
4
167
)
t h e I n - N o r t o S-N v i b r a t i o n s .
I n S N .2FeCl~ t h e v e r y
4 4
o
FeCl^
( v sym.(Ga-Cl)=
weak b a n d a t 2 2 8 cm ^ t o Ga-N v i b r a t i o n .
4
at
1
t o Ga-Cl v i b r a t i o n s , a n d
I n S N ^ . 2 l n C l g , t h e band a t 3 6 1 cm
at
c o m p l e x e s show
adducts o f
By a n a l o g y w i t h
other
-132-
a d d u c t s , i t may h a v e a s t r u c t u r e w i t h m o n o d e n t a t e
In the f a rinfrared
s p e c t r u m o f S^N^.PhBClg t h e s t r o n g b a n d
a t 420 i s e i t h e r due t o S-N
at
360 cm
1
i s assigned t o
o r B-N v i b r a t i o n .
S-N as u s u a l .
a t 314 a n d 282 a r e a s s i g n e d t o
S N
4
Q C 1
adducts, (
The
B - C l by a n a l o g y w i t h
a s s v i n
structure of S N .2AlBr
4
The s t r o n g
4
3
appears
bands
The s t r o n g b a n d s
2
' d e f o r m a t i o n = 330 cm
- 1 47a
d e f o r m a t i o n 230 cm
)
4
S.N..
4 4
1
>
other
B C l ^ sym.
t o be d i f f e r e n t
from t h e above a d d u c t s , s i n c e t h e i n f r a r e d spectrum i s d i f f e r e n t
(Table 2 ) .
The l o w s o l u b i l i t y
and r e l a t i v e l y
p o i n t o f t h i s adduct i n d i c a t e s t h a t
of t h e type ( S ^ N ^ A l B r g ^ . A l B r
.
high
melting
i t may h a v e a n i o n i c
The n e a r i n f r a r e d
structure
s p e c t r u m shows
t h r e e s t r o n g p e a k s a t 1 1 2 6 , 869 a n d 473 i n a d d i t i o n t o o t h e r
weak p e a k s .
cm
-1
S i n c e i n t h e complex
A l B r ^ . E t g O , t h e b a n d a t 445
h a s b e e n a s s i g n e d t o A l - B r s t r e t c h i n g mode
a t 438 i n S N . 2 A l B r ^ i s a s s i g n e d t o
4
4
bands a t 1126 a n d 869 cm
infrared
1
v
Al-Br.
are assigned t o
171
, t h e band
The v e r y
S-N.
strong
I n the f a r
s p e c t r u m o f t h i s a d d u c t a s t r o n g b a n d a t 349 cm * c a n
be a s s i g n e d t o
A l - B r ( c f . A l - B r i n BrCN — » A l B r
absorbs a t
o
3 4 1 and 445 cm
The
1
).
s t r u c t u r e s o f S.N.. T e C l . a n d S.N..SeCl„
4 4
4
4 4
4
The
infrared
infrared
s p e c t r u m o f S.N„.TeCl. i s s i m i l a r t o t h e
4 4
4
s p e c t r u m o f S.N
^1
TC
.SbCl , as shown b e l o w :
D
-133-
S N .SbCl
1058 v s , 975 v s , 807 v s , 786 v s , 722 ms, 682 s , 6 5 1 w, 623 v s ,
4 4
5
563 w, 5 1 1 v s cm
S.N
.TeCl
1047 v s , 966 v s , 8 0 6 s , 7 6 0 v s , 727 vw, 671ms, 635ms, 613ms, 563 w,
-I
SN
500 v s , cm
In the f a rinfrared
spectrum o f S N . T e C l
4
4
there are only
4 >
t h r e e b a n d s , t w o s t r o n g a n d b r o a d bands a t 360 a n d 2 5 1 cm
weak band a t 225 cm
due t o c o m b i n a t i o n
N
^4 4
n
a
v
e
-1
1
168,169
;
S
N
4
^»
4
4 <
TeCl
4
s t r o n g b r o a d b a n d a t 360 may be
i n this region (TeCl ;
i s probably
347 s
161
) or i t
v
may o n l y b e due
c a u s e d by T e - C l a n d Te-N
vibrations.
i n the near i n f r a r e d
spectrum o f
c a n be done i n t h e same way as i n t h e c a s e o f S N .SbCl,..
The s t r u c t u r e
4
of S N .SeCl
4
4
4
may be e i t h e r
145
SeCl. ethylenediamine
o r i o n i c as i n SeCl
,2py
4
138
4
3
or[(S N ) SeCl ]
4
i n s o l u b i l i t y i n i n e r t organic
structure.
4
s i x c o o r d i n a t e as i n
[S N -SeCl ]
Its
358 v s
4
The b r o a d band i n t h e r e g i o n 22-286 cm ^ c e n t r e d
The a s s i g n m e n t o f f r e q u e n c i e s
S N
and a
o f S-N a n d T e - C l modes s i n c e b o t h T e C l ^ a n d
t o S-N v i b r a t i o n .
2 5 1 cm
The v e r y
s t r o n g a b s o r p t i o n bands
a n d 347 v s cm
at
-1
1
4
2
2
s o l v e n t s may i n d i c a t e
I n their discussion of the infrared
Cl"
2 +
SeCl
an
2
6
"
ionic
spectrum o f SeCl ,
4
-134-
169
G e o r g e , K a t s a r o s a n d Wynne
v i b r a t i o n a l data
spectra
nature
of
concluded t h a t t n e avaij.aojLtj
a r e i n accord w i t h t h e presence o f SeClg
i n solid
+
SeCl^ b u t a r e i n c o n c l u s i v e r e g a r d i n g t h e
o f t h e anionic species.
Since t h e f a r i n f r a r e d
((CH_).N) .SeCl_ y i e l d s absorptions
0
spectrum
1
a t 294 a n d 184 cm
w h i c h a r e a b s e n t i n S.N..SeCl. i t seems more l i k e l y t h a t
4 4
4'
4 4
- -4
s t r u c t u r e o f t h e type ( S N . S e C l ) C l .
f
J
S
N
, S e C
1
n
a
s
a
n
i
o
n
i
c
+
4
In
4
3
t h e f a r i n f r a r e d s p e c t r u m o f S N . S e C l , t h e b a n d s a t 383
4
4
4
an
is
a s s i g n e d to/S-N v i b r a t i o n , because S N
4
mode a t 347 cm
1
w h i c h may h a v e s h i f t e d
4
h a s S-N b a n d i n g
t o 383 cm
c o o r d i n a t i o n , o r i t may be d u e t o t h e c o u p l i n g
S-N modes.
due
The b a n d 403 cm
on
o f Se-Cl and
may be a n a d d i t i o n a l S-N band
t o c o o r d i n a t i o n o r i t may be d u e t o Se-N v i b r a t i o n .
solid SeCl
4
The
shows a b s o r p t i o n b a n d s a t : 3 7 1 v s , 348 v s , 275 s,
medium s t r o n g
at
1
1
(broad)
a n d 205 w e a k , t h e r e f o r e ,
t h e bands
337 s , 309 s a n d medium s t r o n g b a n d s b r o a d i n t h e r e g i o n
1
260-217 cm
a r e assigned t o Se-Cl.vibrations.
The s t r u c t u r e s o f S^N^.WBr^, S ^ . W C l , , a n d S„N. .W0C1„(?)
4 4
4' 4 4
4
4 4
4
The
h a l i d e s WX
4
(X= h a l o g e n ) f o r m
a number o f c o m p l e x e s
o f t h e t y p e WX .2L ( L = m o n o d e n t a t e : p y r i d i n e , R C N d i m e t h y l
4
sulphoxide
The
173
r
) and WX »L(L=
4
complexes a r e o b t a i n e d
higher
halides.
173
bidentate:2,2'-bipyridyl)
e i t h e r from
t h e t e t r a h a l i d e s o r from
-135-
The
i n f r a r e d s p e c t r a o f S.N„,WBr„ a n d S.N..WC1^ a r e
4 4
4
4 4
4
T
different
f r o m t h e i n f r a r e d s p e c t r u m o f S N .SbCl .
4 4
o
virtue o f the chelating
the tendency
f o r WC1
coordination,
4
By
n a t u r e o f t h e l i g a n d and on account o f
and WBr
4
t o achieve s i x
t h e adducts S N » W B r
4
4
and S N .WC1
4
4
4
six coordinate structures, with bidentate S N
4
4
4
may h a v e
( c f . MX .2,2'4
bipyridyl).
The i n f r a r e d s p e c t r u m o f t h e c o m p l e x o b t a i n e d
and W 0 C 1
4
shows some s i m i l a r i t y w i t h
S N .WBr
4
and S N .WC1
4
4
4
4
4
4
different
S N
4
4
.WOCl^.
4
4
(but with
5
4
4
).
structure
i s easily
reduced,
The s t r u c t u r e o f t h e l a t t e r may b e s i m i l a r t o
147
WOXg.2,2'-bipyridyl complexes
oxytetrahalides
4
1
1 0 0 0 ( v s ) cm
f r o m S N . S b C l ) o r , s i n c e W0C1
4
S N
the i n f r a r e d spectra o f
( m a j o r peak a t
T h i s compound may b e S N . W 0 C 1
from
(formed
i n reactions o f the
o f t u n g s t e n w i t h b i p y r i d y l , and w h i c h c o n t a i n
six coordinate tungsten).
I n t h e f a r i n f r a r e d s p e c t r u m o f S N .WC1 , t h e band a t
4
406 cm
broad
4
4
may b e d u e t o e i t h e r S-N o r W-N v i b r a t i o n .
band i n t h e r e g i o n 286-385
S-N v i b r a t i o n s
(
i s probably
c a u s e d b y W-N a n d
—1
161
S-N ( d e f o r m a t i o n ) = 347 cm
= 355 cm S i m i l a r l y
i n S N .WBr
4
4
4
in S N
t h e b a n d a t 405 cm
t o e i t h e r S-N o r W-N v i b r a t i o n s a n d t h e a b s o r p t i o n s
270-357 may b e due t o c o m b i n a t i o n s
The s t r o n g
4
1
4
, vW-ClCstretching)
may be due
i n the region
o f S-N a n d W-Br modes.
-136The
preparation
and
reactions
of t r i t h i a z y l
trichloride
174
Baumgarten
has
reported
that pyridine reacts
with
s u l p h u r y l c h l o r i d e t o g i v e a complex o i l p r o d u c t , w h i c h
was
CSL
t h o u g h t t o be
has
(CgHgNqjOSOgCl and
b e e n r e p e a t e d by
product of the
ratio
was
of the
Banister
formula
(CgHgNCl> S0 .
128*
2
oily
(CgHj^OgSOgClg, i r r e s p e c t i v e o f t h e
mole
By
Moore
analogy w i t h t h e above r e a c t i o n , i t
decided t o study the Lewis a c i d behaviour of s u l p h u r y l
towards t e t r a s u l p h u r
no
tetranitride.
adduct i s formed but
This i s not
I t was
trithiazyl
3
as
70).
i s used
e.g.
case,
a
(page
chloride
a c h l o r i n a t i n g a g e n t i n a number o f r e a c t i o n s ,
Ph AsCl
acts
trichloride
s u r p r i s i n g , because s u l p h u r y l
chloride
found t h a t i n t h i s
sulphurylchloride slowly
c h l o r i n a t i n g agent t o give
by
reaction
and / o b t a i n e d a n
reactants.
and
This
2
as
Ph As+SO C I -*
.
2
T r i t h i a z y l t r i c h l o r i d e may be p r e p a r e d by t h e m e t h o d d e s c r i b e d
127
103
117
Demarcay
and Meuwsen
and r e v i s e d by S c h r o d e r and G l e m s e r
,
o f p a s s i n g c h l o r i n e t h r o u g h a s u s p e n s i o n o f S^N^ i n an
inert
103
solvent
o r by
t h e m e t h o d d e s c r i b e d by
Meuwsen
and
revised
by
104
Jolly
and
Maguire
SgNgClg.
Jolly
p o i n t o f 91°C,
4
4
and
solid
Maguire p r e p a r e d SgN^Clg, w i t h a
melting
from S N C L
Glemser r e p o r t e d
from S N
and
i n v o l v i n g the c h l o r i n a t i o n of the
a melting
chlorine.
and
chlorine, while
p o i n t of
Trithiazyl
Schroder
and
162.5°C f o r t h e SgNgClg p r e p a r e d
t r i c h l o r i d e obtained from
the
-137-
r e a c t i o n o f s u l p h u r y l c h l o r i d e and
that of Jolly
and
Magulre.
S^N^ c l o s e l y
T h i s compound has
o f 89-91°C ( d e c o m p . ) b e f o r e
lowering
of melting point
I t has
i s not
d e p r e s s i o n o f m e l t i n g p o i n t by
significant
but
by
i s decomposition catalysed
We
a melting
r e c r y s t a l l i s a t i o n , whereas
o
r e c r y s t a l l i s e d SgN^Clg m e l t e d a t 93-94 C.
that this
resembles
also prepared t r i t h i a z y l
small
point
the
been p r o p o s e d
principally
due
91
to
amounts o f i m p u r i t i e s ,
amounts o f i m p u r i t i e s .
trichloride
f r o m S^N^
and
117
c h l o r i n e by
t h e method d e s c r i b e d
previously
, but
observed
the i n f r a r e d spectrum of the product v a r i e s remarkably w i t h
experimental conditions.
is
obtained
following
l a r g e volume o f t h e
(ii)
(iii)
small
inert
(below)
under
the
solvent
i n w h i c h S^N^ i s
dissolved.
slow r a t e of c h l o r i n a t i o n
short
filter
time or c h l o r i n a t i o n u n t i l
as
s o o n as
a clear red
t h e volume o f t h e s o l v e n t
and
i n f r a r e d spectrum
the
conditions:
suspended or
If
simplest
i f t h e c h l o r i n a t i o n o f S.N.
i s c a r r i e d out
4 4
(i)
dissolved;
The
that
a l l t h e S^N^ i s
solution is
i n which S N
4
t h e r a t e o f c h l o r i n a t i o n i s f a s t and
4
obtained.
i s suspended i s
f o r a longer
a f t e r t h e s t a g e when a c l e a r r e d
s o l u t i o n i s obtained,
gives
r e c r y s t a l l i s a t i o n from carbon
a p r o d u c t w h i c h even a f t e r
t e t r a c h l o r i d e has a much more c o m p l e x i n f r a r e d s p e c t r u m
section ( i i ) below)
the
time
.
reaction
(see
-138-
The compound
o b t a i n e d by s l o w c h l o r i n a t i o n
suspension o r d i l u t e s o l u t i o n )
CC1 ).
The i n f r a r e d
4
the
infrared
from S N
4
4
m e l t e d a t 89-91°C
a n d SOgClgj t h o u g h t h e peak
than f o r the l a t t e r .
4
2
t r i c h l o r i d e prepared
1015 cm
due t o d i f f e r e n c e
The c r y s t a l l i n e form i s i d e n t i c a l
Wiegers m o n o c l i n i c
(from S N /C1 )
4
4
c
X
11.23 X
6.13 R
a
90
/3
99.2° - .2
y
90
5.55
b
was b r o a d e r
107 108
p r o d u c t as s t u d i e d by W i e g e r s a n d Vos
'
Sample s y s t e m
a
1
T h i s was a l m o s t c e r t a i n l y
in p a r t i c l e size i n the mull.
4
(recryst.
s p e c t r u m o f t h i s compound was s i m i l a r t o
spectrum o f t h e t r i t h i a z y l
to the S N /C1
( o f S^N^
Space g r o u p
mols/cell
The i n f r a r e d
5.54
^
(S^/SOgClg)
R
- .02
11.14 £
- .01
6.13
X
90
99.5
90
P2/m
1
P2
1 7
monoclinic
- .01
P2 /m
or
2
Hazell
o r P2
]L
2
1
2
s p e c t r u m o f S^N^Cl^ o b t a i n e d f r o m S N
(slow c h l o r i n a t i o n )
4
orS N
4
1018 v s , 6 9 8 ms, 6 2 1 w ( b r ) ,
4
4
+ SOgClg showed t h e f o l l o w i n g
( 5 1 4 ms, 4 8 8 ms) ( b r ) ,
+ Clg
peaks:
380 w, 320 w ( b r ) .
-139The h i g h e s t f r e q u e n c y a b s o r p t i o n a t 1018 cm
a n S-N
1
i s assigned t o
s t r e t c h i n g f r e q u e n c y , t h e h i g h e s t b a n d s i n o t h e r SN
-
s y s t e m s o c c u r a t : 1325 cm
1085 cm
-1
(SgNgFg)
97
s t r e t c h i n g frequency
on account
1
(NSC1)
, 925 cm
-1
<
93
S
, 1153 cm
N
4
)
4
161
T
•
-1
h
1
(S N C l )
4 3
e
higher
S-N
i n S^N^Cl^ c o m p a r e d w i t h S^N^ i s e x p e c t e d
o f t h e h i g h e r S-N
bond o r d e r ( s u l p h u r - n i t r o g e n
0
7
The medium s t r o n g b a n d a t 698 cm
1
d i s t a n c e s a r e : 1.60& i n S N C I
1
,
1
8
5
3
a n d 1.62A i n S N
0
) .
i s probably a s t r e t c h i n g
t h a n a b e n d i n g mode ( v ( s t r e t c h i n g
h i g h e s t f r e q u e n c y bend
0
bond)
rather
1
i n S^N^ i s a t 696 cm , t h e
v ( d e f o r m a t i o n ) i s a t 347 cm "*"), w h e r e a s
1
t h e weak ( b r o a d ) b a n d a t 6 2 1 cm
cannot
be a s s i g n e d w i t h
certainty,
156
b e c a u s e S-Cl a n d S-N modes a p p e a r i n t h i s r e g i o n
s t r o n g b r o a d b a n d i n t h e r e g i o n 526-477 cm
488 cm
1
may be a s s i g n e d
assigned
= 347 cm
t o NSC1
(from S N
t o S-N
1
w i t h p e a k s a t 514 a n d
3
i s a s s i g n e d a t 414 cm
of S N Cl
The medium
t o S-Cl s t r e t c h i n g , b e c a u s e S-Cl s t r e t c h i n g
- I
9
i n NSC1
1
.
.
In the f a r infrared
a n d SO C l . ) t h e weak b a n d a t 380 cm
b e n d i n g mode b y a n a l o g y w i t h S N ^ (
4
w h e r e a s t h e weak b r o a d
S-N
b a n d c e n t r e d a t 320 cm
- 1 93
( v NSC1 ( b e n d i n g ) = 273 cm
) .
Mass s p e c t r u m o f S„N„C1
O
m/e
spectrum
relative
o
1
is
deformation)
1
i s assigned
o
intensity
assignment
32
43
S
46
262
SN
64
100
S„
-140-
a s s i gninent
m/e
c intensity
78
240
92
372
S_N
138
242
S-N
150
S_N_C1
170
S_N_C1
174
210
( i i ) T h e r a p i d c h l o r i n a t i o n o f S^N^ w i t h c h l o r i n e g a v e a p r o d u c t
which apparently
contains
bubbled a t a very
a new compound.
fast rate through S N
4
Chlorine
suspension i n carbon
4
t e t r a c h l o r i d e a n d a t room t e m p e r a t u r e ( p a g e 7 2 ) .
was p r e p a r e d t w i c e ,
different
and
This
compound
b u t each t i m e t h e a n a l y t i c a l f i g u r e s were
( p a g e 7 2 ) a n d i t was n o t p o s s i b l e
f o r t h i s compound.
g a s was
However i t a p p e a r s
a compound c o n t a i n i n g
t o give
to consist
definite
formula
o f S^N^Cl^
t w o c y c l o t r i t h i a z y l r i n g s a s shown
b e l o w ( a n a l y t i c a l f i g u r e s c o r r e s p o n d t o a 2:3 m i x t u r e ) ;
CI
CI
N
N
N
N
CI
CI
The o u t s t a n d i n g
difference
i nthe i s o l a t i o n procedure i s
that t h i s product p r e c i p i t a t e s o u t ; ( t h i s
reaction s o l u t i o n i s stronger;
i s n o t j u s t because t h e
s i m i l a r q u a n t i t i e s o f S N +CC1
s o l u t i o n were used as i n t h e u s u a l
4
(NSC1)„
preparation).
4
4
-141A r e l a t i v e l y l a r g e number o f e x t r a p e a k s a p p e a r i n t h e i n f r a r e d
s p e c t r u m and t h e s e a r e r e t a i n e d o n c r y s t a l l i s a t i o n .
The
i n f r a r e d spectrum i s d i f f e r e n t from S N CI , the comparison
i s given below,
S N Cl
g
6
4
: 1011
v s , 943
w ( s h ) , 893
687
v s , 6 7 1 v w ( s h ) , 662
517
w ( s h ) , 504 ms,
All
b a n d 546
cannot
are assigned
t o S-N
( 5 1 4 ms,
488
stretching
ms)
cm
^ may
be a s s i g n e d
t o S-Cl s t r e t c h i n g mode.
t r i c h l o r i d e and C l
2
t h r o u g h t h e s o l u t i o n , i t was
f u r t h e r change.
product
to
.
The
vS-S
The
strong
strong
certainty,
or
C0:-
t r i c h l o r i d e o b t a i n e d f r o m S .N
of the evaporated
vibrations,
o t h e r s u l p h u r n i t r o g e n compounds ( p . 1 3 9
d i s s o l v e d i n a l a r g e v o l u m e o f C C l ^ and
spectrum
any
1
be a s s i g n e d w i t h
When t r i t h i a z y l
bubbled
vs,
.
modes a p p e a r i n t h e r e g i o n 4 0 0 * 5 0 0 cm
( i i i ) Trithiazyl
was
cm
w i t h S^N^Cl^ and
i s p r o b a b l y due
b a n d a t 662
1
cm
ms, 546
v s , 698 ms, 6 2 1 w ( b r ) ,
medium s t r o n g b r o a d b a n d a t 452
b e c a u s e S-S
v w ( s h ) , 576
w(sh)
.
t h e b a n d s a b o v e 680
by a n a l o g y
The
1
v s , 625
452 m s ( b r )
SgNgClg ( f r om S ^ / S O C l g ) : 1018
( b r ) cm
m s ( s h ) , 7 8 1 w ( s h ) , 699
and SO
c h l o r i n e gas was
observed
from the
slowly
infrared
t h a t S^N^Cl^ does n o t
H o w e v e r , t h e compound t e n t a t i v e l y
CI
undergo
proposed
as S„N_C1. i s t h e m a j o r p r o d u c t i n a r e a c t i o n o f S_N„C1., ( f r o m
fc> o 4
o j o
S^N^/SO^Clg) w i t h c a r b o n m o n o x i d e , g i v i n g a s m a l l amount o f S^N^Cl.
).
-14 2-
The
mechanism o f t h e f o r m a t i o n o f SgNgCl^ appears t o be complex,
178
b u t may b e a s f o l l o w s
Clc
(1) S N
4
4
+ Cl
> S N C1
2
3
(2) S N C1 + S N C1
3
3
3
3
3
>
3
S N C1
6
6
4
t h e f o r m a t i o n o f S_N.C1. may w e l l d e p e n d u p o n a b u i l d up o f
6 6 4
c o n c e n t r a t i o n o f S N C I o r some o t h e r
o o
incompletely chlorinated
s u l p h u r - n i t r o g e n s p e c i e s as f o l l o w s :
Fast
-» s o l u t i o n
4 4
MED.
red
S
N
3 3
C
S
slower
appreciably
i f s o l i d S„N-C1„
. 6 6
4
precipitate
out
yellow
N
3 3
C 1
3
m.p.89-91 C
Reactions o f t r i t h i a z y l
yellow
1
MED.
S
Fast
intermediate
trichloride
(from S N
4
4
N
6 6
C 1
4
m.p. 5 8 - 6 4 C
(decomp.)
and SOClg):
(a) Attempted p r e p a r a t i o n o f sulphanuric c h l o r i d e from
trithiazyl trichloride
The
isolation
preparation o f sulphanuric
chloride involvest h e
and p y r o l y s i s o f t h e e x t r e m e l y h y g r o s c o p i c
trichloro-
179
phosphazosulphuryl c h l o r i d e
.
The t r i c h l o r o p h o s p h a z o s u l p h u r y l
c h l o r i d e does n o t p y r o l y s e t o g i v e s u l p h a n u r i c
is
impure.
Alternatively
a very poor y i e l d
sulphur
trioxide.
sulphanuric
c h l o r i d e i f t h e sample
c h l o r i d e c a n be o b t a i n e d i n
by h e a t i n g t h e p a l e y e l l o w a d d u c t o f SgNgClg w i t h
-14 3-
Since (NSCD^ i s a r e l a t i v e l y
synthesis of sulphanuric chloride
t r i c h l o r i d e was a t t e m p t e d .
simple preparation
by t h e o x i d a t i o n
the
of
trithiazyl
a
The u s e o f SeO^ a n d
s
t
h
e
o x i d i s i n g a g e n t s were u n s u c c e s s f u l , because i n each case t h e
o x i d i s i n g a g e n t g a v e a new r e a c t i o n p r o d u c t , w h i c h ( f r o m
r.
s p e c t r u m ) was n o t s u l p h a n u r i c c h l o r i d e .
Trithiazyl
the i .
trichloride
did
n o t u n d e r g o any o x i d a t i o n , when a m i x t u r e o f m o l e c u l a r
and
o z o n e was b u b b l e d t h r o u g h a s o l u t i o n i n C C l ^ a t r o o m
oxygen
t e m p e r a t u r e o r a t 60°C.
Failure of trithiazyl
undergo d i r e c t
w i t h m o l e c u l a r oxygen i s i n c o n t r a s t
to
e
the reaction
-S-
S
N
H
4 4 4
oxidation
trichloride to
t h a t occurs w i t h other sulphur n i t r o g e n
110-120°C '
(
H
N
S
0
)
(b) Reaction of t r i t h i a z y l
mercury and p y r i d i n e
a-Sulphanuric chloride
compounds
4
trichloride with
reacts
with
diphenyl
diphenylmercury
180
to
f o r m c l i p h e n y l s u l p h a n u r i c c h l o r i d e , NgSgOgCl(CgH,. ) g
It
was t h o u g h t o p r e p a r e t h e a n a l o g o u s compound S g N g C ^ P h ) ^
by
the reaction
of t r i t h i a z y l
t r i c h l o r i d e with diphenyl
mercury.
H o w e v e r , i t was f o u n d t h a t d i p h e n y l m e r c u r y g i v e s a n a d d u c t
3 3 3 (S N Cl3->Hg(Ph) ).
S
N
with
C 1
3
3
2
By a n a l o g y w i t h t h e r e a c t i o n
of sulphanuric chloride
with
128
pyridine
, i t was d e c i d e d t o s t u d y t h e r e a c t i o n
trithiazyl
t r i c h l o r i d e and p y r i d i n e .
reacted with pyridine
t o give
Trithiazyl
a pale yellow s o l i d .
between t h e
trichloride
The
infrared
-144-
s p e c t r u m showed r e t e n t i o n o f t h e SN r i n g ,
f r e q u e n c i e s were s l i g h t .
The e x a c t
shifts
stdbhiometry
e s t a b l i s h e d on account o f v a r i a b l e analyses
The
i n the
i s not
( p . 77
)
ab»ve t w o r e a c t i o n s e x h i b i t i n g t h e d o n o r a n d
acceptor
behaviour
of trithiazyl
trichloride.
(c) Reaction o f t r i t h i a z y l t r i c h l o r i d e w i t h epibromohydrin,
e p i c h l o r o h y d r i n , e t h y l e n e oxide and b u t y l e n e oxide
181
Peters
and Kharasch
between s u l p h u r y l h a l i d e s
have s t u d i e d t h e r e a c t i o n
and epoxides e.g. e t h y l e n e
oxide
r e a c t s w i t h 2 , 4 - d i n i t r o b e n z e n e s u l p h e n y l c h l o r i d e t o g i v e Cl.CHg.
CHgOSCgH,..
alcohols
Since t r i t h i a z y l
t r i c h l o r i d e reacts vigorously with
(not reported i nexperimental
section) t o give
m i x t u r e s , i t was h o p e d t h a t e p o x i d e s w o u l d g i v e
esters without ring
cleavage.
ethylene oxide, butylene
compounds.
o x i d e a l l a p p a r e n t l y gave t h e r e q u i r e d
Epibromohydrin
e t h y l e n e o x i d e and b u t y l e n e
S_N C l
infrared
and e p i c h l o r o h y d r i n gave w h i t e
were o b t a i n e d
solid
i n t h e case o f
oxide.
spectra o f these
(O.CH CHCH B r )
trithiatriazene
Epibromhydrin, epichlorohydrin,
compounds w h e r e a s r e d o i l p r o d u c t s
The
complex
compounds a r e g i v e n
below,
1429 vw, 1 3 7 0 v s , 1299 vw, 1266 vw, 1235 vw,
1220
vw, 1205 vw, 1176 vw, 1104 vw, 1047 w ( s h ) ,
1036
v s , 1011 s, 990 v s , 962 s, 952 s ( s h ) ,
9 0 1 w ( s h ) , 885 v s , 8 7 0 s , 855 v w ( s h ) ,
(sh),
848 vw
826 v s , 7 8 1 ms, 769 v s , 746 s , 719 v s ,
-145-
694 s , 685 s , 667 s , 637 ms, 623 ms, 617 w
( s h ) , 597 s , 564 ms, 532 vw, 526 vw, 516 vw,
504 ms, 489 ms, 435 ms, 423 s , 4000 v w ( s h ) ,
388 v s , 361 s , 348 w, 323 ms, 274 vw, 253 w,
240 ms cm .
1
SN
O
CI
O
.(O.CH .CH.CH C I )
O
£t
£t
1342 vw, 1290 vw, 1258 vw, 1250 vw, 1212 vw,
O
1188 vw, 1149 vw, 1099 vw, 1053 v w ( s h ) , 1036 v s
1020 s , 990 v s , 962 v s , 901 v w ( s h ) , 885 v s ,
855
s(sh),
833 v s , 787 w ( s h ) , 775 v s , 763 v w ( s h
730 v s , 709 vw, 699 ms, 676 s , 658 s , 570 s ,
544 s , 521 v w ( s h ) , 513 s , 495 ms, 442 ms,
428 s , 408 ms, 392 s , 377 s , 347 s , 331 ms,
276
s , 258 ms, 245 s , 227 m s ( b r ) , 216 vw,
213 vw cm
S N Cl .(O.CH -CH )
3
3
3
2
2
1
.
1453 v w ( s h ) , 1430 w, 1379 vw, 1307 ms, 1258 vw
3
(sh),
876
1198 vw, 1136 v w ( s h ) , 1042 v s , 995 v s ,
v s , 855 v s , 766 w ( s h ) , 722 w ( s h ) , 707 v s ,
667 v s , 536 vw, 392 ms cm
SN
O
CI
O
.(O.CH -CH.CH .CH )
O
£t
Ct
1471 ms, 1439 v w ( s h ) ,
1
.
1372 v w ( s h ) , 1370 w,
O O
1312
w, 1252 vw, 1205 vw, 1042 v s , 980 v w ( s h ) ,
957 v s , 917 s , 866 s , 791 v s , 741 s ( b r ) ,
694 v w ( b r ) , 673 v s ( b r ) ,
1
395 vw, 387 vw c m .
556 vw, 420 ms, 402 vw,
-146-
The a s s i g n m e n t
compounds c a n n o t
modes o c c u r
o f t h e i n f r a r e d a c t i v e bands i n t h e s e
be done w i t h c e r t a i n t y b e c a u s e S-N
i n t h e same r e g i o n i n w h i c h e p o x i d e s
vibrational
give
absorption
bands e . g . i n e t h y l e n e o x i d e t h e bands a t 1165, 1265 and 865
182
are
a s s o c i a t e d w i t h t h e epoxy group
(d) R e a c t i o n of t r i t h i a z y l
.
t r i c h l o r i d e with
nitriles
125
I t was c o n s i d e r e d
likely
to react
that t r i t h i a z y l
i n ( a t l e a s t ) t h r e e ways:
trichloride i s
( i ) as a sulphenyl
c h l o r i d e , RSC1, i . e . a s a n a c i d c h l o r i d e o f t h e h y p o t h e t i c a l
acid
(NS-OH)^ ( s e e r e f .
reactions).
183 f o r a r e v i e w o f s u l p h e n y l h a l i d e
( i i ) a s a s o u r c e o f N=S-C1 a t
s u f f i c i e n t l y high to cause s i g n i f i c a n t
3NSC1.
temperatures
dissociation:
S^N^Cl^
The t h i a z y l c h l o r i d e monomer s h o u l d t h e n be a b l e t o
copolymerise with other unsaturated
systems
c o n t a i n i n g CC,CN o r
CS m u l t i p l e bonds, and ( i i i ) r e a c t i o n w i t h X-H
bonds ( e l i m i n a t i o n
of HC1).
O l e f i n s c a n r e a c t i n a l l t h r e e ways, c h l o r i n a t e d o l e f i n s
as
( i ) and ( i i ) ; c o n s e q u e n t l y
t r i c h l o r i d e and t e t r a c h l o r o
125
d e t a i l by B a n i s t e r
was
t h e r e a c t i o n between
trithiazyl
e t h y l e n e was s t u d i e d i n some more
.; a compound o f e m p i r i c a l f o r m u l a
S^i^C^Cl^
isolated.
The f i r s t
r e a c t i o n i n the n i t r i l e s e r i e s , v i z . the r e a c t i o n
between t r i t h i a z y l
t r i c h l o r i d e and t r i c h l o r o a c e t o n i t r i l e
was
-147-
initially
performed
to check
above were p o s s i b l e .
I t was
o b t a i n e d from S ^ N ^ C l ^ and
light
i f a r e a c t i o n of t h e type ( i i )
( e . g . by c o m p a r i n g
a l s o hoped t h a t t h e p r o d u c t ( s )
t r i c h l o r o a c e t o n i t r i l e might
i n f r a r e d s p e c t r a ) on t h e S N C I /C
O
reaction.
the
A fully
possibility
shed some
c h l o r i n a t e d n i t r i l e was
o
O
CI
«
chosen because
T:
of
o f c o m p l i c a t i o n s a r i s i n g due t o s i m u l t a n e o u s
184
r e a c t i o n s of type ( i i i ) ,
C 1 C H - CHN + P C 1
0
e.g.
» C 1 C = C ( C 1 ) - N=PC1
C
0
| Cl
2
(from P C 1 )
5
ClgC - C C 1
(a)
+ HC1
0
- N = PC1 .
2
3
R e a c t i o n between S N.C1
and C1J2.CN>
T r i t h i a z y l t r i c h l oO r i«Jd e o ( S N «/ S o0 C 1 ) was
4
4
2
2
found n o t t o
r e a c t w i t h S^N^-Glg a t room t e m p e r a t u r e ; a r e a c t i o n
temperature
o
of
60 C was
c h o s e n by a n a l o g y w i t h t h e r e a c t i o n between S N C I
125
and C C I
changes
.
The r e a c t i o n s o l u t i o n s l o w l y u n d e r g o e s
colour
from g r e e n t o p a l e y e l l o w t o r e d and a y e l l o w c r y s t a l l i n e
p r o d u c t was o b t a i n e d w h i c h was found t o be i d e n t i c a l t o t h e
2 2 2 4
3 3 3/ 2 4 (
change w h i c h may be a s c r i b e d t o t h e i n t e r m e d i a t e f o r m a t i o n i n
seem
s o l u t i o n o f monomeric t h i a z y l t r i c h l o r i d e does n o t / v e r y l i k e l y
S
N
C
since
C 1
o
b
t
a
i
n
e
d
f
r
o
m
S
N
C 1
C
C 1
p
a
g
e
8
5
T
n
e
( i ) t h e b r i g h t g r e e n c o l o u r o f t h e s o l u t i o n and
c
o
l
o
u
r
(ii)
o 91
p e r c e p t i b l e d i s s o c i a t i o n i n vacuum commences a t 70-80 C
-148-
T h i s a g r e e s w i t h t h e p r o p o s a l t h a t monomeric t h i a z y l
c h l o r i d e does n o t form i n s o l u t i o n u n l e s s a t h i g h t e m p e r a t u r e s
A n a l y s e s a r e g i v e n below (same b a t c h o f compound
9 1
(above 7 0 ° C ) .
analysed
a t Durham).
Calculated
Found
anal.l
anal
2.
S
N
C
2 2 2
C 1
4
S
N
C
2 2 2
C 1
S
5
N
C
2 3 2
C 1
C
9.59
9.99
9.53
8.19
7.81
CI
55.89
52.80
55.04
60.34
57.72
N
11.60
10.85
10.85
9.54
13.66
S
24.75
21.98
24.80
21.81
20.81
101.83
86.28
Total
Structure
and t h e i n f r a r e d s p e c t r u m o f SgNgCgCl^
The m.,p.(decomp. above 100°C) and t h e i n f r a r e d s p e c t r u m
o f t h i s compound i s i d e n t i c a l t o t h e i n f r a r e d s p e c t r u m o f t h e
p r o d u c t o f t h e SgNgClg and C C 1
2
The f o l l o w i n g
4
reaction
(M.P. 205-208 decomp.)
s t r u c t u r e s a r e p r o p o s e d on t h e b a s i s o f t h e
information discussed
below:
CC1
CC1
CC1
CC1
C
Cl
Cl
N
\
N
(I)
/
N
N
\
N
/
S
N
S
(II)
(III)
5
-149-
ci c - cci
3
2
.N
N;
•N
cci -cci
2
N
CC1,
5
CC1,
3
(V)
(IV)
Structure
(IV) suffers
difficult
t o s e e how
Similarly
i t does not seem l i k e l y
arise
from t h e d i s a d v a n t a g e
i t could a r i s e
from S^N^Cl^/Cl^CCN.
l o c a l i z e d C=N
( 1 6 3 0 - 1 6 9 0 cm
The
—1
)
that i t i s
from S_N C I / C C 1 .
0
that s t r u c t u r e (V) could
i n f r a r e d s p e c t r u m shows
182
o r C=C
no
p e a k s (1620-1645 cm
u n l e s s t h e a b s o r p t i o n s happen t o be v e r y weak (C=N
and
C=C
absorptions a r e o f t e n weak).
a t 1302
and
1270
between t h a t e x p e c t e d
for
is
intermediate i n frequency
s i n g l e bond (1100 cm
and
CN
-1
) and
The
a C=N
d o u b l e bond (1600
s o c o u l d be r i n g v i b r a t i o n ( s ) p r e d o m i n a n t l y
)
185
1
cm
aC-N
t o 1700
cm
-1
)
42
associated with
stretching.
:
I n v i e w of t h e low s o l u b i l i t y
J
(or
doublet
—1
o f S-,N,_C_C1., i n n o n - p o l a r
2 2 2
4
low p o l a r i t y ) o r g a n i c s o l v e n t s and
cannot
be s u b l i m e d
i n vacuum u n t i l
v e r y low v o l a t i l i t y ( i t
100°C and
o c c u r s ) , the i o n i c s t r u c t u r e appears
then
t o be more
decomposition
likely.
'<
Such a s t r u c t u r e
i s analogous with the s t r u c t u r e s
o f S„N C l
3 2 2
6
i
187
and
4-phenyl-l,2-dithiolium iodide, S C Phi.
Further evidence
comes from a s t u d y
v
sym
for a structure
c o n t a i n i n g a C C l ^ group
o f t h e i n f r a r e d s p e c t r u m o f t h i s compound.
CC1„ and
CC1_ i n C1 C.CN o c c u r a t 787 and 491 cm
3
asym
3
3
188
1
0
respectively
(781 and 483 cm
and p e a k s a p p r o x i m a t e l y
1
i n these
) occur i n SgNgCgCl^
t h e r e g i o n 833-741 cm
1
The s t r o n g band i n
i s assigned to v
CC1_ by
sym
with t r i c h l o r o a c e t o n i t r i l e .
positions
analogy
o
S i m i l a r l y t h e medium s t r o n g
b r o a d band i n t h e r e g i o n 500-465 c e n t r e d a t 483 w i t h
a t 495 and 471 cm
1
i s assigned to v
CC1„.
sym
band a t 1052 cm
may
shoulders
The v e r y
strong
3
be due t o e i t h e r S=N o r C-N
since
—
t r i c h l o r o a c e t o n i t r i l e absorbs
The s t r o n g band a t 543 cm
1
i n t h i s r e g i o n ( v C-C = 1000 cm
cannot
be a s s i g n e d w i t h
1 189
)
certainty.
t
( b ) R e a c t i o n between SgNgClg and Bu CN
Trithiazyl
t r i c h l o r i d e was found n o t t o r e a c t
t e r t i a r y b u t y l c y a n i d e a t room t e m p e r a t u r e
reaction
reaction,
temperature
was c h o s e n by a n a l o g y
with
( f o r 24 h o u r s ) .
A 58°C
w i t h t h e Cl^CCN
a g o l d e n y e l l o w p r e c i p i t a t e was o b t a i n e d
(page 8 4 ) .
The a n a l y t i c a l f i g u r e s a r e g i v e n on page 151, (same b a t c h o f compounds),
CM
rH
oCO
CO
-151
X
o
•
CM
O
CO
CO
S5
•
CM
CO
CO
CO
•
CO
CM
CO
00«
co
o
•
O
•
co
CM
i-H
CM
O
co
•
o
o
CM
co
m
t>•
CO
r-1
CM
CO
O
in
O
CO
CM
CM
•»
CM
i-l
oCO
CO
X
u
CM
+>
«i
rH
3
•
CO
CM
CO
•
•*
rH
O
CO
O
rH
<a
o
CO
co
CM
S5
•o
<b
CO
co
•
m
CO
X
O
m
•
o
•
CO
CM
CJ
CM
•
CO
rH
•
i-l
m
•
CM
CO
CM
co
u
CJJ
i-(
•H
CD
S
r-\
co
10
3
en
U
A
CO
-P
CM CO
cn
CM
^
•
•
CO
•
m
l-
m
O
CM
co
m
CD
•
co
•
•
CD
CO
CM
O
l>
rH
CO
m
oo
i-H
m•
00
rH og
cd
C
cd
e
cd
3
-a
c
3
o
Q
o
CD
+>
a)
•
co
CM
•
CO
•
CO
CO
•
rH
rH
•
rH
CO
rH
O
en•
O
cd
a
cd
o
CO
Eh
-152-
It
analogy
for
i s likely
t h a t t h i s compound i s S N C ( C H ) C 1 ,
2
a n C
w i t h SgNgCgCl^
t h i s compound.
with the i n f r a r e d
'
The
s
m
a
i i^-
r
and
at
855
551
cm
1
3
considered
s p e c t r u m shows some
s p e c t r u m o f S N„C„C1
£i
855
1
cm
).
The
S-N, w h i l e t h e peak a t 551
( c ) The
cm
similarity
( t h e p e a k s a t 543,
cannot
r e a c t i o n between S N C l
Trithiazyl
trichloride
was
gave f o u r p r o d u c t s
to be t h e same.
two
The
2 and
may
be due
be a s s i g n e d w i t h
and
The
f i r s t product
to
certainty,
benzonitrile
with
r e a c t i o n a t about 60°C
of w h i c h ( p r o d u c t s 2 and
s o l u t i o n d u r i n g r e a c t i o n and
1
SgNgC^CH^gCl
found not t o r e a c t
b e n z o n i t r i l e a t room t e m p e r a t u r e .
676
4
£»
peak a t 733 cm
1
by
3
i n S g N g C g C ^ a l s o a p p e a r i n t h e presumed
733 and
to products
2
s t r u c t u r e s c a n be
infrared
£i
2
settles
h a s an i n f r a r e d
3, page 8 8 ) p r o v e d
down from t h e r e d
spectrum
similar
3 but w i t h e x t r a p e a k s i n t h e r e g i o n 794-767
w h i c h a r e l o s t on r e c r y s t a l l i s a t i o n
from PhCN or S 0 C l
o
cm
(though
the l a t t e r r e c r y s t a l l i s a t i o n
g i v e s a d d i t i o n a l a b s o r p t i o n a t 510 cm
Thus a f t e r
from PhCN p r o d u c t
product
recrystallisation
2 (the c r y s t a l s
r e a c t i o n ) and
product
the f i l t r a t e ) .
to
t h e ClgCCN and
cm
* one ~
frit
552
cm
during
t h a t d e p o s i t on c o o l i n g
l ' ) , 2 and
i . r . s i m i l a r i t i e s (two
(CHg)gCN p r o d u c t s
t h e s e t h r e e compounds.
the f i l t e r
1 (recrystallised
a n a l y s e s but
833
near
3 (the c r y s t a l s
Products
give s a t i s f a c t o r y
between 910 and
that c o l l e c t
1 i s t h e same a s
1
and
suggest
one
near
similar
3 do
not
absorptions
700 cm
1
structures
)
for
1
),
-153-
Product
filtering
4 was o b t a i n e d
the product
from t h e f i l t r a t e
3 ) by e v a p o r a t i o n
(left
to dryness.
after
A
dark-
y e l l o w . p r e c i p i t a t e was o b t a i n e d w h i c h was r e c r y s t a l l i s e d
C C l ^ o r CHgClg.
from
A f t e r r e c r y s t a l l i s a t i o n t h e compound was p a l e
y e l l o w and a n a l y s e s (page 8 8 ) c o r r e s p o n d
t o an e m p i r i c a l f o r m u l a :
(NSCl) .PhCN
3
The
i n f r a r e d s p e c t r u m o f t h i s compound was d i f f e r e n t
other products
( 1 and 2 ) .
t h i s compound by a n a l o g y
from
An 8-membered r i n g i s p r o p o s e d f o r
with
(NSF)^.
Numerous C-H a b s o r p t i o n s o c c u r between 1660-740 cm ^ a s
i n PhCN, though t h e s t r o n g a b s o r p t i o n s a t 1342, 1179, 910 cm
may i n d i c a t e s u p e r i m p o s e d
CN and/or
at
t h e c h a r a c t e r i s t i c peaks a s s o c i a t e d
701 and 790 a r e p r o b a b l y
with mono-substituted
(CH
deformation)
SN.
1
benzene d e r i v a t i v e s
and 758-747 cm
-1
of
1
493, 473, 419 cm .
these.
( u s u a l l y a t 694-701 cm
,
.185.189
(CC s t r e t c h i n g )
'
.
s i n g l e a b s o r p t i o n i n t h e r e g i o n 588-500 cm
525,
The s t r o n g p e a k s
1
The
i s r e p l a c e d by f o u r :
S C I may be r e s p o n s i b l e f o r one o r more
-154APPENDIX 1
157
C a l c u l a t i o n s of force
constants
G o r d y ' s r u l e : - A r e l a t i o n o f t h e form,
k = aN ( X . X / d M + b
A
has
fi
been found t o h o l d a c c u r a t e l y
f o r a l a r g e number o f
m o l e c u l e s i n t h e i r ground s t a t e s .
force
X
B
Here k i s t h e bond
stretching
c o n s t a n t , d t h e bond l e n g t h ,
N t h e bond o r d e r , and X and
A
a r e t h e e l e c t r o n e g a t i v i t i e s o f t h e bonded atoms.
k
«5
i s measured i n dynes/cm x 10
and
b have t h e v a l u e s
molecules e x h i b i t i n g
and d i n Angstrom u n i t s , a
1.67 and 0.30 r e s p e c t i v e l y , f o r s t a b l e
t h e i r normal c o v a l e n c i e s ,
w h i c h b o t h bonded atoms h a v e o n l y one e l e c t r o n
except those i n
i n t h e i r valency
shell.
Thus s i n c e N-Sb
= 2.17A*
X ( N ) = 3.07 ( A l l r e d - R o c h o w )
X ( S b ) = 1.82 ( A l l r e d - R o c h o w )
B
A
and
N = 1
T h e r e f o r e , t h e (N-Sb) f o r c e
constant =
2 3
1.67 ( 3 . 0 7 x 1.82/2.17 ) + 0.30
4
5
= 2.2 x 10
Now
Where
dyne/cm.
v Sb-N = 1303.16 ( A
A
)^
= force constant = k
r e d u c e d mass
jj
-155-
^
m
^
m
i 2
m
, where m
and
m
a r e atomic weights
i 2
and
Sb-N
Sb(121.75) r e s p e c t i v e l y ) .
= 1303.16 ( 2 . 2 x 0.07959)
= 545
cm
*
S i m i l a r l y u s i n g t h e v a l u e s of e l e c t r o n e g a t i v e s o f 3.04
n i t r o g e n and
o f 565
cm
of N(14.007)
m
2.05
was
for
f o r antimony ( P a u l i n g - t y p e v a l u e s ) , a v a l u e
the
obtained for/Sb-N s t r e t c h i n g frequency.
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