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3 0 0 N orth Z e e b R o a d , A nn Arbor, Ml 4 8 1 0 6 - 1 3 4 6 U S A
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O r d e r N u m b e r 8913668
Studies on the syntheses, reactivities an d stru c tu re s of
ru th e n iu m nitrosyl complexes containing chelating triphosphines
Lee, Ik-Mo, P h.D .
The Ohio State University, 1989
UMI
300 N. Zeeb Rd.
Ann Arbor, MI 48106
Studies on the Syntheses, Reactivities and Structures of Ruthenium
Nitrosyl Complexes containing Chelating Triphosphines
D issertation
Presented in Partial Fulfillment of the Requirements for
the Degree Doctor of Philosophy in the Graduate
School of The Ohio State University
Ik-Mo Lee, M. S.
The Ohio State University
1989
Approved by
Dissertation Committee:
D. W. Meek
A. Wojcicki
E. P. Schram
B. E. Bursten
Advisor
Department of Chemistry
C La
Co-Advisor
Department of Chemistry
To my wife, Mi-Hey and son, Byoung-Hoon
and our parents
ACKNOWLEDGMENTS
I express sincere appreciation to the late Dr. Devon W. Meek for his
guidance, insight and endless support throughout this research. His
warm and kind personality as a human and a scientist has earned
my respect. I want to show my special thanks to Dr. Andrew Wojcicki
for his special attention and caring to the late stages of this research
and for discussions about my research topic. I also appreciate the
valuable
suggestions
and
com m ents
from
other m em bers
of my
advisory committee, Drs. Bruce E. Bursten and Eugene P. Schram. I
wish to express my gratitude to Mr. Carl Engelm an for running
num erous NMR experim ents and allowing me to access to many
modern FT-NMR techniques. Special thanks are expressed to the past
and present M eek group members for many discussions and much
encouragem ent. I heartily appreciate Ms. K elle Z eiher for patient
correcting of most of this manuscripts. I want to show my deep love
and appreciation
to my wife and son and our parents for their
patience, encouragem ent and financial support. At last, I thank Mr.
A1 W hite for the neat typing of this dissertation and the Korean
graduate students for their discussions and encouragem ent.
VITA
August 27, 1956
Born- Inchon, Korea
1979.
B. S.(Chemical Technology) ,
Seoul National University,
Seoul, Korea
1981.
M. S.(Chemical Technology)
Seoul National University
Seoul, Korea
1 9 8 1 -1 9 8 4
Full-tim e
Instructor
Korea M ilitary Academy
Seoul, Korea
1 9 8 4 -1 9 8 7
Teaching Associate
The Ohio State University
Columbus, Ohio
1 9 8 7 -1 9 8 8
Research Associate
The Ohio State University
Columbus, Ohio
PUBLICATIONS AND PRESENTATIONS
"S yntheses,
R eactiv ities
and
Structures
of
R uthenium
N itrosyl
Complexes of Chelating Triphosphines",Lee, I. M.;Meek, D. W., National
M eeting of the American Chemical Society, Toronto, Canada, June,
1988
"Study on the Therm al Characteristics of the A blative Com posite
Materials",Lee, I. M.;Lim, K. C. ;Choi, J. H. ;Kim, D. C. ;Chung, K. H.,
Hwarangdae Laboratory, Korean Military Academy, July, 1984
"Study on the Catalytic Oxidation of Carbon by Using Metal Oxides",
Lee, I. M.;Shin, Y. K.,Bulletin of Engineering, Seoul National University,
1981
FIELDS OF STUDY
M ajor Field: Inorganic Chemistry
Studies in Coordination Chemistry: Dr. Devon W. Meek
v
TABLE OF CONTENTS
P age
A c k n o w led g em en ts
iii
V ita
iv
List of Tables
viii
List of Figures
x
L ist of Abbreviations
xvii
C h a p te r
I. INTRODUCTION
A. General
1
B. Bonding of NO and Structure
3
C. Synthetic Method
17
D. Reactions
20
E. Applications
30
H. STATEMENT OF RESEARCH PROBLEM
32
III. EXPERIMENTAL
A. General Procedure
34
B. Synthesis and Reactions of RuH(NO)(Cyttp)
35
C. Synthesis and Reactions of [RuH2 (N O )(Cyttp)]BF 4
D. Synthesis and Reactions of RuH(NO)(ttp)
vi
49
54
E. Synthesis and Reactions of RuH(NO)(etp)
55
F. Synthesis and Reactions of [RuH2 (N O )(etp)]BF 4
57
G. Synthesis and Reactions of RuCl(NO)(Cyttp)
58
H. Synthesis of Vinylidene Complex
60
IV. RESULTS AND DISCUSSION
A. Structures of RuH(NO)P 3
6
1
B. Structures of [RuH 2 (N O )P 3 ]BF 4 and Reactionswith L
8 8
C. Structures and Reactions of RuC 1(NO)P 3
103
D. Reactions between Ruthenium Hydridonitrosyl
Complexes and Alkynes.
119
E. Oxidative Addition Reactions of RuH(NO)P 3
206
F. Insertion Reactions of C 0 2 -like Molecules.
23
8
V. CONCLUSIONS
261
REFERENCES
262
vii
LIST OF TABLES
T ab le
P age
1. 31P NMR Parameters for Ruthenium Hydridonitrosyl
Com plexes
6
4
6
5
7
8
2. lH NMR and IR Data for Ruthenium Hydridonitrosyl
Com plexes
3. Selected Bond Distances and Angles of RuH(NO)(Cyttp)
4.
Comparison of Selected Bond Distances and Angles of
Triphosphine Com plexes
5.
6
3iP NMR Parameters of fac-RuH(NO)(ttp) for Simulation
8
5
8
5
. Thermodynamic Function Values of Three Exchange
Processes of
7.
fac-RuH(NO)(ttp)
Selected Bond Distances and Angles of
[Ru(PMe 3 )(NO)(Cyttp)]BF 4
8
78
98
. 3iP NMR Parameters for the Products of Reactions
between RuH(NO)(etp) and HBF 4 in Different Solvents
99
9-. 3IP NMR and IR Data for the Selected [Ru(L)(NO)P 3 ]BF 4
100
10. Spectroscopic Data for RuC1(NO)P3
106
11. Selected Bond Distances and Angles of RuCl(NO)(Cyttp)
112
12. Spectroscopic Data for RuCl2 L 3 (CO)
106
13. Geometry of Alkenyl Complexes Derived from
Term inal A cetylenes
125
14. Geometry of Alkenyl Complexes Derived from
Internal
A cetylenes
127
15.
Spectroscopic Data for
Ru(C 2 R)(NO)(Cyttp)
139
16.
31P NMR Parameters
for Ru(alkenyl)(NO)P 3
156
17.
NMR and IR Spectra Data for Ru(alkenyl)(NO)P 3
157
18.
13C NMR Parameters
for Ru(alkenyl)(N 0 )P 3
158
19.
Spectroscopic Data of
[Ru(alkenyl)(NO)(CHCl2 )(Cyttp)]Cl
159
20. 31P and ! H NMR Parameters of
[Ru(rj2 -acetylene)(NO)P 3 ]BF 4
2 01
21. 13C NMR and IR Spectra Data for
[Ru(rj2 -acetylene)(NO)P 3 ]BF 4
202
22. Spectroscopic Data of Oxidative
Addition Reaction Products
23. Spectroscopic Data for Ru(allene-H)(NO)(Cyttp)
ix
241
260
LIST OF FIGURES
F igures
1. Molecular Orbital Diagram for M(NO) (a) and M(NO )2 (b)
2. The Correlation Diagram Relating MO's of Linear and
Bent
6
-coordinate MNO Complexes
3. The Correlation Diagram Relating MO's of Linear and
Bent 5-coordinate MNO Complexes
4. The Correlation Diagram Relating MO's of Td and Square
Planar 4-coordinate MNO Complexes
5. The Correlation Diagram of cis-M(NO)2 XL 2 ( {M (N 0 ) 2 }8)
with a ( l b j ) 2 Electron Configuration
6
. Crystal Structures of Isomers of [IrH(N 0 )(PPh 3 ) 3 ][C 1 0 4 ]
7. Proposed Structures of MH(N 0 )L 3
8
. 31p{lH} NMR Spectrum of RuH(NO)(Cyttp) in C 6 D 6 at
101.252 MHz
9.
!H NMR Spectrum of RuH(NO)(Cyttp) in CgDg at 250.133MHz
10.
3 1 P{!H}
NMR Spectrum of RuH(NO)(etp) in C 6 D 6 at
101.252M H z
11. iH NMR Spectrum of RuH(NO)(etp) in C 6 D 6 at 250.133 MHz
12. IR Spectra of RuH(NO)(Cyttp) and RuD(NO)(Cyttp) in
Nujol Mull
13. IR Spectra of RuH(NO)(etp) and RuD(NO)(etp) in Nujol Mull
14. ( a j^ C p H } NMR Spectrum of RuH(NO)(Cyttp) in C 6 D 6 at
62.896 MHz and (b) NOE Spectrum(Irradiated at the
hydride peaks) in C 6 D s at 250.133 MHz
72
15. Possible Structures of RuH(NO)(Cyttp)
73
16. Possible Structures of RuH(NO)(etp)
74
17. X-ray Crystal Structure of RuH(NO)(Cyttp)
77
18. Variable Temperature
3 1 P{*H}
NMR Spectra of RuH(NO)(ttp)
in CD 2 CI 2 at 101.252 MHz (a) Experimental (b) Calculation
8
2
8
3
8
4
19. Variable Temperature *H NMR Spectra of RuH(NO)(ttp) in
C D 2 CI 2 at 250.133 MHz (a) Experimental (b) Calculation
20. Proposed Fluxional Mechanism of fac-RuH(NO)(ttp)
21. Variable Temperature
3 1 P { 1 H)
NMR Spectra of
[RuH 2 (NO)(Cyttp)]BF 4 in CD2 C12 at 101.252 MHz
90
22. Variable Temperature JH NMR Spectra and T i of
[RuH 2 (NO)(Cyttp)]BF 4 in CD2 C12 at 250.133 MHz
91
23. IR Spectrum of [RuH2 (NO)(Cyttp)]BF 4 in CH2 C12
92
24. X-ray Crystal Structure of [Ru(PMe3 )(N O )(etp)]Cl C 6 H 6
96
25. 31P{ 1H) NMR Spectrum of [Ru(PMe3 )(NO)(Cyttp)BF 4 in
A ceto n e-d 6 at 101.252 MHz.
101
26. 3lp{lH } NMR Spectrum of [Ru(PMe3 )(NO)(etp)]BF 4 in
A ceto n e-d 6 at 101.252 MHz
27.
3 1 P{!H}
102
NMR Spectra of RuCl(NO)(Cyttp)(a) and
RuCl(NO)(ttp)(b) in CD 2 C12 at 101.252 MHz
107
28. IR Spectra of RuCl(NO)(Cyttp)(a) and RuCl(NO)(ttp)(b) in
Nujol Mull
108
29. X-ray Crystal Structure of RuCl(NO)(Cyttp) ( Isomer A
30.
3 1 P{!H}
)
111
NMR Spectrum of [RuCl(NO)(Cyttp)][BF 4 ]2 in
A ceto n e-d 6 at 101.252 MHz
115
xi
31. IR Spectrum of [RuCl(NO)(Cyttp)][BF 4 ]2 in Nujol Mull
116
32. M olecular Orbital Interactions between Acetylenes and
120
Metal Ceter
33. 3lp{lH } NMR Spectrum of Ru(CCPh)(NO)(Cyttp) in C 6 D 6 at
132
101.252 MHz
34. !H NMR Spectra of Ru(CCPh)(NO)(Cyttp) (a) before and
(b) after treatment of acetone in C 6 D 6 at 250.133 MHz
133
35. 13c {1H} DEPT NMR Spectra of Ru(CCPh)(NO)(Cyttp) in CD 2 C12
134
at 62.896 MHz
36. IR Spectrum of Ru(CCPh)(NO)(Cyttp) in Nujol Mull
135
37. 3lp{lH ) NMR Spectrum of Ru(C(CH 2 )C 0 2 Et)(N0)(Cyttp) in C 6 D 6
141
at 101.252 MHz
38. lH NMR Spectrum of Ru(C(CH 2 )C 0 2 Et)(NO)(Cyttp) in CgDg at
142
250.133M H z
39. lH NMR Spectrum of the Product of the Reaction between
RuD(NO)(Cyttp) and CHCC02Et in C 6 D 6 at 250.133 MHz
143
40. 13C{1H} DEPT NMR Spectra of Ru(C(CH 2 )C 0 2 Et)(N0)(Cyttp) in
144
CD 2 C12 at 62.896 MHz
41. IR Spectrum of Ru(C(CH 2 )C 0 2 Et)(N0)(Cyttp) in Nujol Mull
145
42. 3lp{lH ) NMR Spectrum of [RuCl(C(CH 2 )C 0 2 Et)(N0)(CyttP)]Cl
151
in CDC13 at 101.252 MHz
43. lH NMR of [Ru(C(CH2 )C 0 2 Et)(N0)(Cyttp)Cl]Cl in CDCI3 at
152
250.133 MHz
44. C-H Correlation Diagram of [Ru(C(CH 2 )C 0 2 Et)Cl(N0)(Cyttp)] in
153
C D a3
45. 13C{1H} DEPT NMR Spectra of [Ru(C(CH2 )C 0 2 Et)Cl(N0)(Cyttp)]
154
in CDCI3 at 62.896 MHz
xii
46. 31p{lH} NMR Spectra of Ru(C(CH 2 )COMe)(NO)(Cyttp) and
Ru(CHCHCOMe)(NO)(Cyttp) in C 6 D 6 at 101.252 MHz
160
47. lH NMR Spectra of Ru(C(CH 2 )COMe)(NO)(Cyttp) and
Ru(CHCHCOMe)(NO)(Cyttp) in C 6 D 6 at 250.133 MHz
1 61
48. 3lp{lH} NMR Spectrum of [RuCl(C(CH2 )COMe)(NO)(Cyttp)]Cl
in CDC13 at 101.252 MHz
162
49. lH NMR Spectrum of [RuCl(C(CH 2 )COMe)(NO)(Cyttp)]Cl
in CDCI3 at 250.133 MHz
50. (a) Normal (b)
13 c { lH
1 63
) DEPT NMR Spectra(Phenyl region only)
of [Ru(CHCl2 )(C(CH 2 )COMe)(NO)(Cyttp)]Cl in CDCI3 at
62.896
MHz
164
51. 3lp{lH ) NMR Spectrum of Ru(CCCOMe)(NO)(Cyttp) in C 6 D 6 at
101.252 MHz
166
52. lH NMR Spectrum of Ru(CCCOMe)(NO)(Cyttp) in CD2 C12 at
250.133 MHz
167
53. 3lp{lH ) NMR Spectrum of Ru(CCCH 2 OH)(NO)(Cyttp) in CD 2 C12
at 101.252 MHz
170
54. lH NMR Spectrum of Ru(CCCH 2 OH)(NO)(Cyttp) in CD2 C12 at
250.133 MHz
171
55. !H NMR Spectrum of Mixture of Ru(CCCH 2 OH)(NO)(Cyttp)
and Ru(CCH 2 CHO)(NO)(Cyttp) in CD2 C12 at 250.133 MHz
172
56. 3lp{lH} NMR Spectrum of Ru(C(C0 2 M e)CH C0 2 M e)(N0)(Cyttp)
in CD 2 C12 at 101.252 MHz
176
57. lH NMR Spectrum of Ru(C(C0 2 M e)C H C 0 2 M e)(N0)(Cyttp) in
CD 2 C12 at 250.133 MHz
17 7
58. 13c{lH} DEPT NMR Spectrum of
R u(C(C0 2 M e)CH C0 2 Me)(N0)(Cyttp) in CD 2 C12 at 62.896 MHz
xiii
17 8
59. C-H Correlation Diagram of Ru(C(C0 2 M e)C H C 0 2 M e)(N0)(Cyttp) 179
60. 13c INEPT Spectrum of Ru(C(C0 2 M e)CH C0 2 M e)(N0)(Cyttp)
in CD 2 C12 ( Carbonyl Region Only)
180
61. 31p{lH) NMR Spectrum of [Ru(CC(H)Ph)(NO)(Cyttp)]BF 4
in CD 2 C12 at 101.252 MHz
1 82
62. lH NMR Spectrum of [Ru(CC(H)Ph)(NO)(Cyttp)]BF 4 in CD2 C12
at 250.133M Hz
183
63. 13C{1H) NMR Spectrum of [Ru(CC(H)Ph)(NO)(Cyttp)]BF 4
in CD 2 C12 at 62.896 MHz( (a) C a , (b) C(3 )
184
64. 3lp{lH} NMR Spectrum of [Ru(C(CH 2 )COMe)(NO)(etp)]
in CD 2 C12 at 101.252 MHz
188
65. 1H NMR Spectrum of [Ru(C(CH 2 )COMe)(NO)(etp>]
in CD 2 C12 at 250.133 MHz
66.
189
13c{lH) DEPT NMR Spectra of [Ru(C(CH 2 )COMe)(NO)(etp)]
in CD 2 C12 at 62.896 MHz
190
67. 13C INEPT NMR Spectrum of [Ru(C(CH 2 )COMe)(NO)(etp)]
in CD 2 C12 at 62.896 MHz
68.
1 91
31p{ lH) NMR Spectrum of [Ru(ti2-(CC0 2 Me) 2 )(N 0)(Cyttp)]BF 4
in CD 2 C12 at 101.252 MHz
1 95
69. !H NMR Spectrum of [Ru(ri2-(CC0 2 Me) 2 )(N 0)(Cyttp)]BF 4
in CD 2 C12 at 250.133 MHz
196
70. 13c{lH} DEPT NMR Spectra of
[Ru(Ti2 -(C C 0 2 Me)2 )(N0)(Cyttp)]BF 4 in CD 2 C12 at 62.896 MHz
1 97
71. IR Spectrum of [Ru(ri2-(CC0 2 M e) 2 (N 0)(C yttp)]B F 4 in
Nujol Mull
198
72. 3lp{lH ) NMR Spectrum of [Ru(ti2-(CC0 2 Me) 2 )(NO)(etp)]BF 4
in CD 2 C12 at 101.252 MHz
203
xiv
73. lH NMR Spectrum of [Ru(Ti2 -(CC 0 2 Me) 2 )(N 0 )(etp)]BF 4
204
in CD 2 C12 at 250.133 MHz
74. 13c{lH} DEPT NMR Spectra of [Ru(ii2-(CC0 2 Me)2 )(NO)(etp)]BF 4
205
in CD 2 C12 at 62.896 MHz
75. 3lp{lH } NMR Spectrum of [RuI2 (NO)(Cyttp)]I in CD2 C12
210
at 101.252 MHz
76. IR Spectrum of [RuI2 (NO)(Cyttp)]I in Nujol Mull
211
77. IR Spectrum of [RuBr2 (NO)(Cyttp)]Br in Nujol Mull
212
78.31p{lH) NMR Spectrum of [RuI(NO)(Cyttp)] in C 6 D 6
215
at 101.252 MHz
79. IR Spectrum of [RuI(NO)(Cyttp)j in Nujol Mull
21 6
80. 3lp{lH } NMR Spectrum of [RuBr(NO)(Cyttp)] in C 6 D 6
21 8
at 101.252 MHz
81. IR Spectrum of [RuBr(NO)(Cyttp)] in Nujol Mull
219
82. 3lp{lH} NMR Spectrum of [Ru(0 2 CCH 3 )(N0)(Cyttp>]
223
in C 6 D 6 at 101.252 MHz
83. lH NMR Spectrum of [Ru(0 2 CCH 3 )(N0)(Cyttp>] in C 6 D 6
224
at 250.133 MHz
84. 13C{lH} DEPT NMR Spectrum of [Ru(0 2 CCH 3 )(N0)(Cyttp)]
in CD 2 C12 at 62.896 MHz( Alkyl Region Only)
85. IR Spectrum of [Ru(0 2 CCH 3 )(N0)(Cyttp)] in Nujol Mull
86.
225
226
3 lp {lH ) NMR Spectrum of [Ru(0 2 CPh)(NO)(Cyttp)]
227
in C 6 De at 101.252 MHz
87. 3lp {lH ) NMR Spectrum of [Ru(0 2 C P hN 0 2 )(N0)(Cyttp>]
22 8
in C 6 D 6 at 101.252 MHz
88.
3lp{lH } NMR Spectrum of [Ru(0PhN 0 2 )(N0)(Cyttp)]
233
in CD 2 C12 at 101.252 MHz
xv
89. *H NMR Spectrum of [Ru(0 PhN 0 2 )(N 0 )(Cyttp)]
234
in CD 2 C12 at 250.133 MHz
90. IR Spectrum of [Ru(0 PhN 0 2 )(N 0 )(Cyttp)] in Nujol Mull
235
91. 31p{lH} NMR Spectrum of [Ru(NO)2 (Cyttp)][BF 4 ]2 in CD 2 C12
239
at 101. 252 MHz
92. IR Spectrum of [Ru(NO)2 (Cyttp)][BF 4 ] 2 in Nujol Mull
240
93. 3lp{lH } NMR Spectrum of [Ru(S2 CH)(NO)(Cyttp)]
245
in CD 2 C12 at 101.252 MHz
94. lH NMR Spectrum of [Ru(S2 CH)(NO)(Cyttp)] in CD2 C12
246
at 250.133 MHz
95. 13C{1H) NMR Spectrum of [Ru(S2 CH)(NO)(Cyttp)]
247
in CD 2 C12 at 62.896 MHz
96. IR Spectrum of [Ru(S2 CH)(NO)(Cyttp)] in Nujol Mull
248
97. *H NMR Spectrum of [Ru(OC(H)NPh)(NO)(Cyttp)]
250
in C 6 D 6 at 250.133 MHz
98. *H NMR Spectrum of [Ru(SC(H)NPh)(NO)(Cyttp)] in C 6 D 6
252
at 250.133 MHz
99. 31p{lH) NMR Spectrum of [Ru(S0 3 H)(N0)(Cyttp)] in CD 2 C12
257
at 101.252 MHz
lOO^H NMR Spectrum of [Ru(S0 3 H)(N 0 )(Cyttp)] in CD2 CI2
258
at 250.133 MHz
101.IR Spectra of [Ru(SC>3 H)(NO)(Cyttp)] and
[R u(S0 3 D)(N0)(Cyttp)] in Nujol Mull
xvi
259
L ist of Abbreviations
C yttp
PPh(CH 2 CH2 CH2 PCy2)2
t tp
PPh(CH 2 CH 2 CH 2 PPh 2)2
e tp
PPh(CH 2 CH 2 PPh 2 )2
L
M onodentate N eutral Ligand
X
Anionic Ligand
Me
M eth y l
Et
E thyl
i-P r
iso p ro p y l
Ph
Phenyl
xvii
Chapter I.
Introduction
G eneral
From molecular orbital (MO) theory, nitric oxide (NO) has one electron
in
the
antibonding
removed.
n -MO
orbital.
Consequently,
it
can
be
easily
( The ionization potential is 9.5 ev.l ) Therefore, it is usually
thought that coordination of NO to a transition metal atom might involve
transfer
of
the
antibonding
electron
from
NO
to
the
metal
atom;
consequently, the concept of a NO+ cation as a coordinated entity in
nitrosyl complexes has been widely accepted.
M + NO
-------------►
M- + NO+
(1)
Despite all the shortcomings of this designation, it proves useful in such
cases
as
the
M-NO
bonding
nature
and
reactivity.
Since
isoelectronic with CO, its synergistic coupling o f cr and
to strong M-NO bonds, like the M-CO bond.
complexes are similar to CO complexes.
closely
related
with
carbonyl
n
NO+ is
bonding leads
Also some reactions of NO
As above, nitrosyl complexes are
com plexes
and
as
Johnson
and
M c C le v e rty l pointed out, the development of this field goes along with
that of metal carbonyl complexes.
CO
Since NO is a better n
acceptor than
it is expected that the M-NO bond would be stronger than M-CO;^
this leads to a decreased reactivity of the M-NO moiety, which has been
blamed
for less activity
complexes.
However,
coordinated
NO
in this
as
the
( Eq. 2 )
field
noble
becomes
compared
nature
to that of carbonyl
of
clear,8»9,10
bonding
and
of
some
the
nitrosyl
0
1
N
N
/
M
M
M
(2)
linear
form
(NO + )
bent
f o r m a l l y , 3 e ' donor
com plexes
are
hydrogenation,
considerably.
(NO")
fo r m a lly , le*
found
and
form
as
useful
donor
ca ta ly sts
fo r
p o ly m erizatio n ,
oxidation, ** the activity in this field has increased
A nother
factor
to
stim ulate
the
study
of
nitrosyl
complexes comes from attempts to reduce the NO gas in exhaust gases
em itted
field
from
internal
com bustion
engines. *0»H
The activity in this
is reflected by the number of literature reviews covering these
nitrosyl complexes.
After the first comprehensive review*
several reviews have been published covering general
structure
and
cluster nitrosyl
bonding;4,14
appeared,
aspects,3>*2,13
synthesis,*5 r e a c tio n s ^ ’*®’* 1 .1 6 ,1 7 ,1 8 and
complexes. *9
Due to the unique bonding modes of NO
ligands, the chemistry of nitrosyl complexes is expected to show some
interesting
aspects
accompanying
modes;
in some cases^0»21
reactions
where nitrosyl
the
interconversion
this actually happens.
complexes
act
as catalysts,
of
these
two
Also, in some
bending
of NO
3
group is proposed for the possible
Moreover, structual
m e c h a n is m .2 2
information about the NO complexes can give some insight on studies of
alkyl diazo c o m p l e x e s ^ which are also flexible and closely related to the
dinitrogen
complexes
nitrogen.
that, in
turn,
are
important in the
fixation
of
Since NO" is isoelectric with N22"* which is the activated form
of N2 , bent NO complexes are directly related with N2
a c tiv a tio n .2 4
To
date, there are relatively few bent NO complexes, but molecular orbital
theory
makes
it possible to propose some rules
where the mode of NO bonding is
chelating
such
triphosphines
as
co n tro l
have
of
Considering the fact that
b e n t.2 5
some
advantages
sto ich io m etry
to predict examples
and
over
monophosphines,
s t e r e o c h e m i s t r y ,
23a t h e
combination o f a triphosphine and a flexible ligand to achieve some
unique
g r o u p ,
coordination
23a,26,27
thoroughly
n itro sy l
structures
been
a
research
topic
in
our
however, the chemistry of the complexes has not been
investigated.
com plexes
investigated;
has
Therefore,
co n tain in g
in
this
ch elatin g
study,
the
chemistry
trip h o sp h in es
w ill
of
be
in addition the bonding modes of the NO ligand during the
reaction and their relationship with the structure will be focused.
Bonding
o f NO
and
Structure
1. n - a c c e p t o r
Since
coordination
confirm ed
by
co m p lex es,
extreme
reservoir).
form
of
NO" was
jn
I b e r s ^ ’2 9
co o rd in ated
form
dje
first
x-ray
proposed
structural
N O '(bent
form)
has
donation
from
the
for II -back
by
S id g w ic k 2
studies
been
8 ancj
of
iridium
regarded
as the
metal
center(electron
Since CO is isoelectric with NO+ , and CO never shows the bent
except
perhaps
one
e x a m p le ^ ®
which
needs
more
precise
4
investigation, the relative n-acceptor ability of NO and CO has been a
debated topic.
The infrared (IR) stretching frequency of CO has been an
excellent tool to monitor the n-backbonding; it is natural to attempt first
to measure the relative II-acceptor ability between CO and NO by use of
IR stretching frequencies or force constants,
that NO is a slightly better
n
Lewis^ 1 first reported
acceptor than CO by measuring the force
constant in the carbonyl series [Ni(CO)4 , Co(CO)3 NO,
M n (C O )(N O )3 ].
in v e stig atin g
F e(C O )2(N O )2,
Later, Taylor32 and Lottes^3 confirmed this report by
the
IR
stretch in g
freq u en cies
in
the
series
of
C o (C O )(N O )L 2 (L=neutral ligand) and a wide variety of nitrosyl carbonyl
com pounds,
resp ectiv ely .
R ecently,
XPS
(X -ray
photoelectron
spectroscopy)
data^ and E i/2 >0x data** were used successfully to confirm
the assumption that NO is a better acceptor than CO.
Structures
Enemark
of
Nitrosyl
and Fcltham
C om plexes4
classified
nitrosyl
complexes
according
to
the
number o f electrons in the {MNO} group and the coordination number
(the number o f electrons in the
{MNO}
electrons, if the NO is regarded as NO+ ).
group is the number of d
Since this classification is
convenient and clear, the following section is organized by this system.
a
6-coordinate
1)
M o n o n itr o s y l
Com plexes
C om p lexes
a) {MNO} 4 >5 -6
Essentially the M-NO linkage is linear
b) {MNO} 7
The nature of the NO is not clear.
5
Only examples in this category are [Fe(das)2 (N 0 )B r][C 104]24 (angle of
M-N-O; 148(2)0), [Fe(das)2(N O)(N CS)][BPh4 ]-(CH3)2CO 21 (158.6(9)°)
and Fe(NO)(TPP)(l-Melm) 36 (140°).
c) {MNO} 8
Essentially, the M-NO group is bent.
2)
D in itro sy l
C om plexes
All complexes in this category are (M(NO)2) ® species.
The two NO's
are cis to each other and essentially linear.
b.
5 -c o o rd in a te
1)
M o n o n itro sy l
C om plexes
C om plexes
a) {MNO} 8
Three
lim iting
structures
for
the
com plexes
in
this
group
are
re p o rte d .
(1) Trigonal bipyramidal (TBP) with a linear NO group in the axial
p o sitio n .
(2) TBP with a linear NO group in the equatorial position.
(3) Square pyramidal (SP) with a bent NO group in the axial position.
b) {NMO} 7
SP with an essentially NO group.
c){M NO} 6
There is only one complex in this category.
[F e (N O )(S 2 C 2 (C N )2 )2 ]-» ^ Where the structure is SP with a linear,
axial NO.
6
2)
D in itr o sy l
C om plexes
There are four examples in this group:
[R u (N O )2 C l(P P h 3 )2 ]P F 6 C 6 H 6 ,37
[O s(N O )2C l(P P h3)2]B F 4,38 and
[Os(OH)(NO)2(PPh3)2]BF4 39 , [RuCl(NO)2{(Ph2P C H 2 )2 -C i8 H io }]B F 4 4 °
have a SP structure with trans phosphines and a linear and a bent
NO group.
C.
4-C oord in ate
1)
M o n o n itr o s y l
Com plexes
C om p lexes
All the known structures are {MNO} ^
geometries
complexes and two limiting
are known.
a) Tetrahedral (Td) Complexes with a linear NO group.
b) Square Planar Complexes with a bent NO group.
Diamagnetic
{MNO}
3 complexes are expected to have square planar
structure with a linear NO group.
2)
D in itr o sy l
C om plexes
All the known structures are also {MNO} *0 complexes and all have Td
geometry and essentially two linear NO groups: however, in one case,
[Rh(N0 )2(PPh3)2][C104] 41, the M-N-0 angle is as low as 158.9(4)°
d.
Others
7
Some
7-coordinate
com plexes
com plexes
are known
but
since
and
some
these
M(NO)3 and M (NO )4
are not
im portant
in
this
research, discussion of these complexes is omitted.
M olecular
Orbital
Theory
For a long time, the coordination modes of the NO ligand and structures
of
th e
n itro sy l
theoretical
com plexes
have
attracted
many
stru ctu ral
and
studies.4’**.25.42 Many of these theoretical studies depend on
calculations
that
use
approxim ate
atomic
basis
sets
or
qualitative
comparisons o f metal and NO orbitals, and it is hard to tell which
parameters govern the bonding modes of NO and structures.
fragm ent
form alism 4 ^
fragments
easily
Recently,
was introduced to see the interaction between
and
H o ffm a n n 2 ^
successfully used this method to set
up some rules about the bonding modes and the site of NO in several
geometries, mainly 5-coordinate mononitrosyl complexes.
F e lth a m 4
exam ined
Encmark and
introduced the concept of {M(NO)n } functional
the
behavior
of
this
group
during
the
group
change
of
and
some
parameters by observing the nature of the highest occupied molecular
orbital (HOMO).
the
coordination
group.
These factors include: 1) the coordination number; 2)
geometry;
and
3)
the
number
of electrons
in
this
Molecular orbitals proposed for {M(NO)n } (n=l,2) are shown in
Fig. 1 and these orbitals are perturbed by the coordination of additional
ligands to the metal.
correlation
For the mononitrosyl complexes, molecular orbital
diagrams for 6, 5, and 4-coordinate geometries and charge of
relative energies of MO with changing the M -N-0 angle are shown in
Figs. 2, 3, and 4, respectively.
8
•4
O-N-M-N-0
D ^
M o le c u la r
o
3"
H -
H -
+ (x
O rb ita ls
L igand O r b ita ls
,o (N O ) )
(O-N
H-O)
( * J ( N O ) ,x z ,x y )
8—»
0
\
* * (N O )
C
• 5o(o
(NO ),*
)
---• *o (t,o (N O ))
r 3»(w *(N O ),x*,jr*)
» "(N O )
2ff
( x z ,x y ,ir * ( N O )
JNO)
:
(HO))
_ ln
(N O )
In
(N O )
: I * ( • (NO))
■ 3<J(e(N O ),z2)
■ 2 ”j ( o * ( N O ) )
• lo(o(N O ))
*
(b)
(a)
Fig.
1
(N O )
Molecular Orbital Diagram for M(NO) (a) and M(NO)2 ( b )
In Fig. 5, a correlation diagram of cis-M (N O ;2X L 2({M (N O )2)
depends on the angle of N-M-N, is shown.
which
This method has been applied
to the polynitrosyl complexes; the authors claim that this method can be
applicable to other systems containing
ligands which have n
systems
and energies of metal d orbitals and of the II * orbitals of the ligand are
sim ilar.
9
*
7 -
■5?
30.
ENERGY
(« )
20 '
>10
■’Witt
9
a 'f o ( K » .s * )
j a ^oQtO) , t ) . -------------------------— ---------------------------------------------------- ■ —
Fig 2
T he correlation
bent
diagram
6-co o rd in atc
—A—
*\
rela tin g
M NO
l b 1l x - - - J )
-
_
lbl . 2- v 2 i
........................t a J ( » 2 - y 2 )
4j | f z 2 )
^ s.
)
^
v
^
^ J e i ' t t x n ) . x x . y z ) >>
2
”*'*
---------------- *
U (xy)
^
_ _ ___________ l b , ( x v )
I b . (xy)
_
y . ? « , < x y .tp 2(S))
_ _
■h«yz.-*(S J;)^
lb (x z.-M X O )) _
—
«.
2 e (xz.vz,-*C :Q )l
__
^
2 e ( x z . y x . - * ( ? < 0 ) ) ,» *
—’
The correlation
bent
2 m" ( k y )
I « ’ ( i p 2 Cl) . i i )
**
Fig. 3
and
V°
—kii
/
x—J
/
3o(-*(sn) , n , \ 7 )
j b c *r>o).xz; .
M O's of lin ear
Com plexes
—A—
/
3«<«2- y 2 >
—
^
diagram
5 -co o rd in ate
relatin g
M NO
->» U ^ C y a . ^ Q i Q ) )
M O’s of lin ear and
com plexes
4
the co rrelation
p la n a r
diagram
relatin g M O 's of Td and
4 -co o rd in a te
MNO
com plexes
-J
<M20V
1.(w* ( H O ? ) /
j*
a
> "
' " * .lb
Fig. 5 C o rrelation
( { M ( N O ) 2 )^ )w ith
diagram
1( x t . i f
( MO))
of cis-M (NO)2 X L 2
a ( I b i ) 2 e le c tr o n
c o n f ig u r a tio n
square
11
In terconversion
The
of
interconversion
pertinent
NO + and
or
NO"
NO+ and
to various catalytic
evidence for conversion
NO" has been recognized as being
However, reported
p r o c e s s e s . 2 2
o f linear into
bent NO
includes
structural
only
two
exam ples:
[Co(das)2(NO)][C104l2 + NCS"
> fCo(das)2(NO) (NCS)][NCS]
TBP, equatorial NO
angle of Co-N-O; 179(2)°
Oh
132(2)°
(3)
NaBPh4
[Fe(NO)(das)2][C104]2+NCS"-------------- >[Fe(das)2(NO)(NCS)][BPh4]-(CH3)2CO
Acetone
SP, axial NO
Oh
(4)
angle of Fe-N-O; 172.8(17)°
158.6(9)°
Also,
Collman 4 4 ,4 5
"hybridization
frequencies
reported
isomers"
depend
on
proposed an equilibrium
linear
and
that
Co(NO)Cl2 ( P R 3 )2 ^
relative
intensities
the experim ental
o f NO
conditions.
exists as
stretching
The
authors
between two conformers, i.e. a TBP with a
NO and a SP with a bent NO, but the x-ray crystal structure^ 5
shows that one form of Co(NO)Cl2 (P M eP h 2)2 has a TBP structure with a
significantly
bent
in t e r p r e ta tio n ^
equatorial
was suggested
NO
(1 6 4 .5 (6 )°).
(bending
plane
Therefore,
of NO
is
another
different).
C ollm an^S reported another example of interconversion of NO+ and NO"
by using
frequencies
N O P F 6 in the RuCI-(NO)2 (P P h 3)2
are observed, as expected,
if 15 jqo
Four NO
stretching
coordinates
in either
position of SP geometry and Eisenberg 58b proposed the mechanism in
Equation 5 to explain these observations.
o
O
kN represents 15 N
(5)
However,
another suggestion 4 (j?q. 6) can explain these experimental
re s u lts:
Cl
Ru( 15NO)CI(PR3)2 +NO
“ 1+
1
P— Ru— P
---------^
* \
*N
N
O
' / 6 V
.0 ~ \*
*N
C k I/ p
p ' ' Ru'~ N D
N
—
c S j J' P
'" 'N O
*N repesents 15N
(6)
Recent
nmR
spectra 47
suggest that the previous mechanism is
favored: however, to explain all the experimental data, one more isomer
should be included as follows (Eq. 7).
13
O
/
*N
I ^
l . * 'P
C l— R if — ND
/
Ru— N
(7 )
5.
C h a r a c te r iz a tio n
a.
In fra red
(IR )
S p ectro sco p y
In spite o f the success of molecular orbital theory in explaining and
correlating the MNO angle with the electronic state and structures of
complexes, a need still exists for a simple diagnostic tool for prediction
o f structure and reactivity.
The NO stretching frequency theory in the
IR spectra has played this role, although no consensus, clear-cut ranges
for linear and bent NO have been proposed.
The first comprehensive
study of the IR spectra of metal nitrosyl complexes has been done by
W ilkinson et.al.48 >49
expected from the NO+ coordination model, the
free NO+ (N O + (S b C l6) ') stretching frequency at 2250 cm"l drops to 15801980 cm‘ l (terminal NO) upon coordination to a metal center.
Bridging
NO stretching frequencies appears at even lower energies (around 1450
c m ‘ l , or even as low as 1328cm’ l in Cp3M n 3 (N O )4; triply bridging NO),
as in the case of CO complexes.
Gans^O suggested that bent NO stretching
frequencies lie in the range between
1515
and
1700 c m 'l , and this
14
overlapping region leads to uncertainty on the nature of NO bonding.
As
G riffith^! proposed,
with:
NO
stretching frequencies
are related
1) the oxidation state and coordination number and
closely
2) the n -
acceptor and a -donor abilities of the other ligands present.
Therefore,
Haymore et. al.23c,52 jjave refined this region by considering the above
facts;
they
proposed
an empirical correction formula and
concluded
that corrected NO frequency of 1610cm"l will be a decision where linear
and bent NO's are distinguished.
similar types
certain
Despite the successful application in
of complexes, caution may be required; however, it is
that these
rules
are useful
in
studies
o f this
field.
After
thorough
investigation, v(RuNO) and 8(RuNO) are assigned to a band
(weak
the
in
IR,
strong
in
the
Raman)
around
600
cm" 1 and an
absorption (weak in the Raman, strong in IR) at lower frequency. 1 ?
Finally,
it
between
is
v(N O)
worth m entioning
and
the
about
electrophilic
the em pirical
reactivity
relationship
o f coordinated
NO.
Bottomly et. al. suggested that nitrosyls with v(NO) greater than 1886cm"
* 53 or
b.
1850cm" * 54,55 wju be susceptible to nucleophilic attack.
P h o to e le c tr o n
Measured
S p ectro sco p y
N -ls binding energy by photoelectron spectroscopy
to the effective charge on the NO group.
prevent
decisive
conclusions;
however,
than 402eV indicates linear NO 4
low er
v alu es.5 6
N -ls
is related
Some contradictory
binding
energy
data
greater
whereas bent NO's generally show
However, as Enmark^
indicates, this energy is not
necessarily related to the geometry and some caution is still required in
interpreting the data.
Jolly^G reported that a rough linear relationship
exists between vNO and N -ls binding energy and insensitivity o f this
15
method is observed to differentiate
between terminal
and bridging NO's.
In conclusion, despite all the efforts to correlate N -ls binding energy
with NO bonding modes (reference 56 and references therein), it is not
always conclusive and more effective methods to determine the bonding
modes of NO are needed.
c.
This
X -ray
is
c r y sta llo g r a p h y
the
only
method
available
coordinated NO group unequivocally.
bent,
~ 1 2 0 ° )
show
( 1 . 9 8 - 1 .
86A).
( 1 . 7 8 - 1 . 5 7 A )
the
bonding
mode
Two extreme forms (linear,
and intermediate forms are reported.
short M-N distances
lengths
to
trans to a linear NO ligand is usually
~ 1 8 0 ° ;
Usually, linear NO has
and bent NO has
It has been
of
longer M-N bond
noticed that the metal ligand bond
s h o r t e n e d . 5 7 > 5 8
but longer metal-
ligand bond trans to bent NO is observed.^ H ow ever,
as
Enem ark
in d icate s,^ the M-N distance and the M-N-0 angle describe the geometry
of the complex, but in themselves do not provide sufficient information
concerning the distribution of charge in the MNO group.
Therefore,
much caution is needed when linear and bent complexes are described
as NO+ and NO" derivatives, respectively.
d. l^ N
nm
R
S pectroscopy
Although x-ray crystal structures show the bonding modes of NO in the
solid state, this does not represent the solution structure sufficiently, * 9
because, especially in 5-coordinate complexes, the energy gap between
SP and TBP geometries is rather small.4.25
The possible use of ^ N
spectroscopy has been integrated as a tool to distinguish between the
two extreme modes of NO bonding.
Despite all the shortcomings of ^ N
16
NMR (low natural abundance
( 0 . 3 6 5 % ) ,
and long relaxation time and low
sensitivity due to negative gyromagnetic ratio ), it appears to be very
useful due to the large downfield shift in the bent nitrosyl ligand, as
compared with the linear one.^9
recent experimental
to
c
o
a lone
m
p
o
u
n
d
This type of down field shift due
r e s u l t s . 4 7 , 6 0 , 6 1 , 6 2
pair located
s ^
The expectation was confirmed by
on
the
nitrogen
is
also
observed
in
diazo
and proposed mechanism of down shift (low energy n ^
n * electronic circulation) was confirmed by using (perfluoroalkyl ) cnitroso
that
the
com pounds.^ *
following
From the available data, G ladfelterl^
four
regions
can
be
found
depending
concluded
upon
the
nature of nitrosyl complexes:
1) Terminal, linear, mononitrosyl complexes
; 8(1 ^N)
350“450 ppm
2) Dinitrosyl complexes
;
510-570
3) Bent, mononitrosyl complexes
;
740-870
4) p-NO complexes
;
750-815
* 8(1 ^N) is shown downfield relative to NH3O), 25°C
Confusion arising from overlap o f regions 3 and 4 can be avoided by
considering the circumstantial evidence.
Also, M in g o s ^
demonstrated
that
the
behavior of
this
method
is
useful
to
explain
controversial
nitrosyl complexes (RuCl(NO)2 (P P h 3)2 ; see section B.4).
o f chemical shift o f
l^ N
is
observed
in
the
linear
Periodic charge
m ononitrosyl
c o m p le x e s ,61,63 too; ^ e shielding tends to increase across the series of
the transition metal and increase down the group.
advanced
NMR techniques
and
relaxation
With the help of
reagents ([Cr(acac)3 ]), there
17
is no doubt that this method will eventually shed light on the nature of
m etal-nitrosyl
complexes.
S ynthetic M ethod
15
As can be seen in this section, a wide variety of NO sources are available;
in addition, some new methods using the new
P P N [N 0 2 ] ^
1. N itric
a.
NO sources
such
as
arc still being explored.
Oxide
A d d u ct
F o rm atio n
MLn+ xN O ----- >M(NO)xLn
This
reaction
occurs
when
MLn
is either a 15- or
17-electron
com plex.
b.
S u b s titu tio n
MLn+ xN O
R eac tio n
> M(NO)xLm + (n-m)L
From an electron counting view, xNO can replace
ligand or x(l-electron ligand + 2-electron ligand).
3
tw o-electron
Theoretically, a
bent NO can replace 1-electron ligand; however, to date, no example
has been reported.
c .R e d u c tiv e
N itr o s y la tio n
In this category, NO functions as a reducing agent.
C0CI2 + 3NO + B + ROH
>1/2 [Co(NO)2CL]2 + BH+ + RONO
(10)
( ref. 65)
M0CI5 + N O
>Mn(NO)2Cl2 + NOC1
( 1 1 ) (ref. 66)
1 8
2. N 0+
The salts of NO+X" (X being a non-coordinating anion such as BF6’ ,P F 6‘ ,
or HS0 4 ") are a source of NO+* N O + is isoelectronic with CO, and similar
reactions
a.
are observed.
A d d ition
Rh(ttp)Cl + N O +
>[Rh(ttp)(NO)Cl],+
Ru(NO)C1L2 + N O +
b.
>[Ru(NO)2C1L2]+
(12) (ref. 23a)
(13) (ref. 38 )
S u b s titu tio n
Usually, CO is the ligand replaced by NO+ but phosphines are also
replaced in some cases.
Fe(CO)3L2 + NO+
>[Fe(NO)(CO)2L2]+
M(NO)L3 + N O +
> [M(NO)2L2]+ (M=Rh, Ir)
(14)(ref. 67)
(15) (ref. 18,68)
3. NOX
The covalent nitrosyl halides NOX generally react by oxidative addition;
however, sometimes X2 formed by reaction (16) also reacts by oxidative
addition:
2NOX
4.
>2NO + X2
(16)
[Ir(COD)Cl]2 + N OX
> (COD)Ir(NO)Cl2
Ni(CO)4 + NOX
>NiNOX2
(18)(ref. 70)
RUH4L3 + NOX
--------> Ru(NO)Cl3L2
(19)(ref. 71)
N -n itr o s o a m id e s
(17)(ref. 69)
19
N -m ethyl-N -nitroso-p-toluene
sulfonam ide,
Diazal,
reacts
with
metal
hydrides to produce metal nitrosyl complexes, and usually removal of
one neutral ligand such as CO and phosphines also occurs.
HMn(CO)5 + Diazal
> M(CO)4NO + CO
(20)(ref.72)
H2RUL4 + D iazal----- > Ru(NO)2L2 + 2L
(21)(ref.73)
Two possible mechanisms (Equations 22 and 23) were proposed for this
re a c tio n :
HM Ln
> HMLn-l + L
HMLn-l + RNO —> [HM(RNO)Ln- l ] ----->M(NO)Ln -i + RH (22) (ref. 74)
or
-L
HMLn + R N O
>H—M Ln-------- > M(NO)Ln-l + RH
: :
(23) (ref. 15)
R -N O
NO2 -/H +
N O + is produced by the following reaction:
N02" + 2H+---------> H2O + NO+
[Ru(L2)(H2 0 )X]+ + NaN02 + HC1
(24)
[Ru(NO)(L2)X]2+
(25)(ref. 74)
L=0-phen, bipy
N a[FeH (C O )4 ] + 2NaN0 2 + 3CH3 C O 2H
3Na02CCH3 + 2H2O
Others
> F e(N O )2 (C O )2 + 2CO +
(26)(ref.75)
20
No transfer reactions,2**
RONO, HNO3 , and some reaction of coordinated
N O 2 ' have been used to produce nitrosyl complexes in some cases.
NO
transfer reactions will be shown in the following section in detail.
E
R eactions
1.
R eactions
a.
of
C oordinated
N u cle o p h ilic
NO
A ttack
One of the best studied reactions in this category is the reaction of
nitroprusside
This
anion
anion
reacts
([Fe(CN )5 ( N O )]2 ") with
with
OH"
to
produce
various
the
nucleophiles.2 2
corresponding
nitro
co m p lex es,[F e(C N )5 (N 0 2 )]^ "I some other complexes are also reported to
follow
the
same
pathw ay,^4,78,79,80
but some reactions give
other
com plexes.
[Ru(NH3)5(NO)]3+ + O H"
> [Ru(NH2)(NH3)4(NO)]2 + -------- >
[(NO)(NH3)4R uNH2(0)NR u(NH3)5]5+
----------------------------------->
[Ru(NH3)5(N2)]2+ + cis-[Ru(OH)(NH3)4 (NO)]2+ + H+
(27) (ref. 81)
[M(NO)(NCMe)2(PPh3)2l2+ + OH" ---------- > [M(NO)(OH)(PPh3)2]+
(M= Rh or I r )
(28) (ref.82)
Alkoxide can also attack NO to give alkylnitrite complexes,^ 8 but in some
c a se s,83 it leads to a 1-electron reduction.
[IrCl3(NO)L2]+ + R O H ----- >[IRCl3(RONO)L2l
(29)
[CpM(NO)2L]+ + RO"
(30)
>[ CpM(NO)2L>
Diazotation occurred when [Ru(bpy)2C l(N O )]2+ reacts with P-R-C6H 4 N H 2
via the following mechanism:^4
Ru(NO)~,2+ + NH2A r ------Ru - N - NH2Ar->2+-£as§»
Ru - N(O) - NHAr-.+ + BH+
RuN = NAr + B + H2O
(31)
21
Azide ion reacts with [Ru(das)2 C l(N O )]2 + to give an azide complex and
N 2 O.
By using a
labelled complex, the following mechanism was
proposed: ®^
.0
Ru
1W
*
N ?;
" l+
Ru—1 5 V
or
N= = N = = N
n 3‘
R u -N3
+
N20
1 +
O
1 6 ^
yN
Ru
+ N2
( 32 )
Finally
it is important to point out the empirical relationship between
v(NO) and the electrophilic nature of the NO ligand, which was discussed
in Section 8.5a, again.
b.
E le c tro p h ilic
Coordinated
NO
A tta ck
shows
reactivity
tow ard
electrophilic
regents,
Electrophilic regents can attack both N 2 0 ,3 9 an(j q 86,87 atoms,
direct attack on NO in the first step has been challenged
too.
but
in some
re a c tio n s:
OsCl(CO)(NO)(PPh3)2 + HC1 —> OsCl2(CO)(NHO)(PPh3>2
O s ( N O ) 2 ( P P h 3)2 + H C 1
(33)
> [ O s ( N O )( N H O ) ( P P h 3 )Cl] -H O —>
[Os(NO)(NHOH)(PPh3)2Cl2l
(34)
Ir(NO)PPh3)3 + 3HC1
(35)
>IrCl3(NH 20H )(PPH 3)2
(O C) 4 Ru;
\
/
22
,C H a
vD
O
R u(C O ) 3
CF3SO3CH3
(OC) 3 R u r ~ |- - ~ R u ( C O
)3
M 0 O )3
\ ; r u ( c o )3
CD
CF 3 S O 3 H
R u(C O ) 3
(OC)3Ru
R u (C 0 )3
[(il5-C5H4Mc)3Mn(NO)4 + HBF4 (or HPF6)
>
[(7l5-C5H4Me)3Mn3(NO)3(^3-NOH)]+
(37)
[Co(das)2(NO)Br]+_H±> [Co(das)2(NHO)Br]2 +
[Co(das)2(NO)]2+ + HBr ----------- > [Co(das)2(NHO)Br]2+
(38)
In equation (38), [Co(das)2 (N O )]2+ does not give the protonated product
and x-ray studies show that [Co(das)2 (N O )]2+ 2^ has a linear NO but
[C o (d a s )2 (N O )B r]+ has a significantly bent NO group.2^
Therefore,
McCleverty proposed the following mechanism:
[ C o ( d a s ) 2 ( N O ) ] 2+ +
B r
> [ C o ( d a s ) 2 B r ( N O ) ] + _ H j>
[Co(das)2(NHO)Br]2+
Actually, OsCl2 (C O )(PPh3)2(NHO) was structrurally characterized.2 9
c.
S u b stitu tio n * 2
(39)
23
G enerally,
NO
does
not
undergo
ligand
substitution
under
normal
conditions, but photolysis of [RuX5 (N O )]2- and [RuCl(bipy)2 (N O )]2 + can
make the reaction proceed.
hv
[RuX5(NO)]2- + H2O ------- > [RuX5(H20)]2- + NO
(40)
hv
[RuCl(bipy)2(NO)]2+ + CH3C N
d.
M igratory Insertion
>[RuCl(bipy)2(CH3CN)]2+ + NO (41)
o f NO to M-C
Bonds
While migratory insertion o f CO into transition metal-carbon bonds is
well studied, migratory insertion of NO is not common.
Since this type
of reaction in zinc alkyl complexes was discovered by F r a n k la n d ^ first,
this
This
reaction also occurs commonly
reaction
was
in
the
in the main group
transition
metal
alkyl
metal
alkyls.
com plexes.
The
structures of [WMe4{0NN(M e)0>2] 90 and [TaMeCl2 {ONN(Me)0 ) 2]91 were
determ ined
another
crystallographically.
exam ple
of
NO
R ecently,
m igration
and
Bergman
studied
9 2 ,9 3
the
reported
mechanism
th o r o u g h ly .
o
0
||
m
r n r /
CpCo
nR
k1
-
CpC o
II
fyl
^ / ^ R
C pC o.
L
R
0
CpCo:
L
He
also
found
elim ination
that this
reaction
does
process
not
is
intram olecular
compete
with
the
and
that
m igration
the
(3 -
reaction.
24
L e g z d in s ^
claimed the first reaction in which NO+ inserts
chromium-methyl
bond.
He
proposed
an
interm olecular
into
a
mechanism
and that the product tautomerizes to a formaldoxime complex.
Cp
+
r v nd
> C r« /
QsJ
|
CH3
ND
n+
C p C r(N 0 )2(N (0 )C H 3)
C pC r(N O )2(CH3)
CP
CN
[
CH3
ND
'N D
+
n+
C pC r(N O )2(N (OH)CH2)
(43)
e.
NO
T ransfer
1)
S im p le
NO
R eaction^ 5
tran sfer
Co(NO)(DMG)2 + M Ln
reaction
Co(DMG)2 + M(NO)Ln
(44)
This type of reaction occurs when nitrosyl acceptor complexes are 15or 17-electron species.
Therefore if MLn is either CoCl2 L 2 » NiClL3 ,
C rC l6^ ‘ »V(CO)6 or Co(DMG)2 , this type of reaction occurs.
2)
NO/
h alogen
in te r c h a n g e
Co(NO)(DMG)2 + MClLn
r ea ctio n
CoC1(DMG)2 + M(NO)Ln
This reaction proceeds when MClLn is 16 electron species.
Examples are shown as follows:
(45)
25
Co(NO)(DMG ) 2 + N i02L 2-------Ni(NO)ClL2 + CoC1(DMG)2
Co(NO)(DMG)2 + RI1L3C I------Rh(N0 )L3 + CoC1(DMG)2
(46)
Co(NO)(DMG ) 2 + R11L3 CI2 -------Ru(N0 )C 1L2 + CoC1(DMG)2 L
3) O ther
R eagents
Ru(NO)2 L2 + RUL3 X 2
2Ru(NO)XL2
(47)(ref. 96)
For the mechanism of this NO transfer reaction, Caulton suggested that
an initial isonitrosyl complex might be involved as follows:
(DMG) 2 Co-N=0 - > MLn ---------- >Co(DMG) 2 + NO — >MLn
(48)
NO — >M Ln-r-g4rran;ge M(NO)Ln
f.
Reactions of NO with CO
2NO + CO
N2O + C O 2
A H 0 2 9 8 = -91.3 Kcal/mole
(49)
AG°298= -78.2 Kcal/mole
Although
this
reaction
is
favorable
therm odynam ically,
rate is very slow in the absence of catalysts.
observed
that
the
reaction
Johnson and Bhadari9 7
[Ir(NO)2 (P P h 3 )2 ]+ can catalyze the above reaction and
Haymore and Ib ers9 8 also reported that some iridium nitrosyl complexes
can
produce
g r o u p s 9 9 . 1 0 0
ruthenium
CO2 and
N2 O in the reaction with CO.
reported on the reactivity o f some rhodium, iridium, and
nitrosyl
com plexes,
and
reactions in the Rh case. Eisenberg
reaction
Later, these
thoroughly
and
then
R h C l3 catalysis in ethanol.
others!® ! also
2 1 C , 1 0 2 , 1 0 3
proposed
the
a j
found
the
studied the
following
same
above
mechanism
for
26
Cl
CC
00
o
NO
00
Cl
00
NO
00
( 5 0 )
00
HO'
Cl
I ^N O
GC— RhCT
I
N
Cl II
o
[R h (N O )2CI2]‘
00
-C 0 2 + h 2o
( 5 1 )
N oO
HoO
O
Rh.
Cl
2.
R eactions
at
the
HO
Cl
M etal
%
Y
'
cr ^ Rh
^ J / 0
S
'
Center**
Cl
27
a.
O xidative
A dd itio n
R eaction
Oxidative addition reaction of the following four types o f reactants have
been studied extensively.
1)
R u C1(NO)(L)2
This compound is a trans, square planar, linear
{RuNO} ^ and more
r e a c tiv e
[M C 1 L 2 (C 0 )]
th a n
is o e le c tr o n ic
[ M C 1 L 2 ( N O ) ] + (M =Rh,
Ir)
c o m p le x e s ,
Im p o rtan t
reac tio n s
are
or
show n
b e i o w . 1 0 4 , 1 0 5 , 1 0 6
R u CIL2(NO)
to s y l
c h lo r id e
HCI
[R u CI2L2(H )(N O )]
/RCOCI \
\
[R u CI3L2(NO)]
(CF3C 0 ) 0
[R u CI2L2(R )(N O )] \
[R u C I(0 2C F 3)(C 0 C F 3)(N 0)]
[R u CI(X2)L2(NO)]
2)
Ru(NO)2 9 6 ’107
RuJNO^Lg
C l2
[R u CIL2(NO)]
[R uC 3(N O)L2]
PhCH 2Br
c f 3c o o -t
[R u(O C O C F 3)3L2(NO)]
[R uB r(C O )L2(NO)]
[R uB r2(C O )2L2]
28
[M (NO)L3 ](M=Co, Rh, I r ) 18,22a, 109
HC1
PhCOCl
[C o C12(N O )L 2]
[C o (N O )(C O )L 2]
[C o I 2(N O )L 2]
( 5 '4 )
MeOH
[C o l(N O )2L2]+ [C o l2L2]
[Rh(NO )L3]
NOPF6
hCOCI
Rh(NO)l2L2 + L Rh(NO)(PhCO)CIL2 +L Rh(NOH)CI3L2
[Rh(NO)2L2]PF6 (5 5 )
Rh(HNO)CI3L2
Rh(NO)(CO)(Ph)CIL + L
Rh(CO)CIL2
29
Mel
lr(M e )(l)(N 0 )l_ 2
lrHX(NO)L2
HX
lrX2(NO )L2
|excess HX
lrX3(NH2OH)L2
4) CpW (CO )2 ( N O ) + l 2 - ^ — > [G p W (N 0 )(C 0 )l2 l
[C p W (N O )l2 l 2
b.
S u b s titu tio n
( 5 7 ) ( r e f .l0 9 )
R eac tio n
Generally, linear NO shortens the trans ligand-metal bondHO’H l
bent NO shows a strong trans
i n f l u e n c e .
18,112
Therefore,
and
stereospecific
products have been obtained by the substitution reaction.
(trans, mer)[RuCl3(NO)L2] _ L > (cis,m er) [RuCl2 (NO)L3]+
(58)
(trans, mer)[ReCl3 (N O )L 2]" _I^_>(cis,mer) [ReCl2(NO)L3]
(59)
30
c.
A dduct
F o rm atio n
[R uC 1(N O )L 2] can react with SO2, CO, O2, olefin and
a l k y n e ^ 4 , 1 1 3
t0
produce an adduct product.
A p p lic a tio n s
1.
H om ogeneous
C ataly sis
A wide variety of olefins undergo oligomerization, polymerization and
hydrogenation reactions in the presence o f nitrosyl complexes.
Pd(II)
and
Pt(II)
catalyzed
oxidations
of
olefins
by
the
Also
following
sch em e.
2PdCl2 + 2NO + H2O
> Pd(NO)Cl + [Pd(N02)Cl3]2‘ + 2H+
[Pd(N0 2 )Cl3]2- + RCH=CH2
> Pd(NO)Cl + RCOCH3 + 2C1‘
( 6 0 )
( 6 1 )
The catalytic oxidation of triphenylphosphine to the oxide by use of
ruthenium nitrosyl complexes such as Ru(N 0)X (02)(PPh3)2 (X=C1, OH, CN
or NCS) or Co complexes, [Co(NO)(saloph)j has been reported.
2.
P o llu tio n
C o n tro l
The basic chemistry was already discussed in the previous section, but
in some cases, especially with
N 2 O.
ruthenium metal, N2 is evolved instead of
B u t l e r ^ attributes this result to the intrinsic property of the Ru-
NO bond.
Under the CO and NO atmosphere, NO can be adsorbed
to the
metal preferentially and there is a great chance of NO being adsorbed
on adjacent sites.
As the result, coupling of two adjacent adsorbed NO's
can produce N2 with high possibility.
31
3.
P recu rso r of N itrido
The
N itro
C o m p o u n d s115
M=N bond is known to be very strong and usually very inert.
Therefore,
A lso
C om pound1^ &
the possibility
cluster
heterogeneous
coordinated
catalysis,
o f new
atomic
and
much
ceramic
species
material
are
effort to
has
been
im portant
introduce
in
sought.
studying
atomic
species
into clusters has been undertaken.
Moreover, oxidation o f NO group
w ith
compounds
m olecular
oxygen
to
nitro
has
drawn
because nitro compounds arc useful as oxygen transfer agents.
attraction
C h a p te r
Although
II
S ta te m en t
hydridocarbonyl
o f R ese arch
complexes
have
P ro b le m
attracted
much
attention
due to their utility in organic syntheses * * ^ and catalytic reactions, 1*7
its
counterpart
unnoticed.
of
hydridonitrosyl
com plexes
have
been
rem aining
Few complexes of this category are known (RuH(NO)L3 ,* 18
I r H ( N O ) ( P P h 3 ) 3 , 119 C p R e ( C O ) ( N O ) H , 120
CpW (N O )2 H 121 a n d
C p W (N O )H (C H 2 S iM e 3 ) , l 22 where L is triphosphine or phosphite and
even
few er
exam ples
re p o r te d . 118,121,123
(form ally,
of
chem istry
of
th ese
com plexes
are
Considering the flexible nature o f NO ligand
3 e ' donor or l e ' donor)
and
rich
chem istry
of
hydride
complexes, it is surprising that the chemistry of this group has not been
investigated
thoroughly
f lu x io n a lity * 18
up
to
date.
and i s o m e r s . S i n c e
This
m ight
chelating
be
due
triphosphine
to
some
ligands
reduce the rate of intramolecular exchange and lim it the number of
chem ically
expected
reasonable
that
pathways
for
the
rearrangem ent,^2^ ’*2^
it is
M H(NO)P3 (P 3 ; chelating triphosphines) might stop or
minimize the fluxional behavior and allowed to be studied easily by
spectroscopic method at the room temperature.
advantages
of
chelating
triphosphines
over
Also there are several
monophosphines
such
as
control o f stoichiometry and coordination number due to less tendency
tow ard
d isso ciatio n .^2 ^ This character appears to be very important to
see the change of bonding modes of NO during the reaction, if any.
32
In
33
other words, if the products follow the EAN (Effective Atomic Number)
rule, the situation of bent NO can be designed by tailoring the ligand
except P3 and NO.
show
the
structures
Moreover, structural determination of MH(NO)P3 will
effect of chelating
triphosphines
on
the
structure
because
of RuH(NO)(PPh3)3 126 and [IrH(NO)(PPh3 )]3 + 41a,127 are
already known.
Since complexes in point have hydride ligands, it is
relevant to compare the reactivities toward small molecules with other
hydride
complexes.
Moreover,
since
structural
depending on the ring size of chelating
change
t r i p h o s p h i n e , 2
was
6 > l 2 4
observed
comparison
of structure, bonding mode of NO and reactivities of Cyttp (or ttp) NO
compounds with etp NO compounds will be examined.
To date, only one
complex containing two flexible ligands (NO and allyl) was reported and
its fluxionality was examined.^2 ^
Therefore, when some flexible ligands
such as NO, RCOO", allyl and alkylazo ligands are introduced to the metal
center with a coordinated NO, the investigation of the consequence will
be interesting.
research
Ruthenium will be chosen as a metal center in this
because
only
com parable
chem istry
of
analogues was reported even though not extensively.
m onophosphine
CHAPTER I I I EX PERIMENTAL
G en eral
P ro ced u res
All re a c tio n s
w e re
te c h n iq u e s .*29
c a rrie d
out by
using
S ch le n k
an d
d ry
box
reag e n t g rad e solvents used in th e e x p erim en t w ere
d rie d b y using co n v e n tio n a l m ethods.* 30
R eagent chem icals w ere
p u rch ased in th e h ig h est p u rity possible and used directly.
RUCI3 XH2O
w as p u rch ased from S trem Chem icals Inc. (N ew b u ry p o rt, MA) ; Cyttp
and ttp w e re p re p a re d b y follow ing th e l i t e r a t ur e * 3 11 and e tp w as
p u rc h a se d
fro m
A ld r ic h
C h e m ic a l
C o .( M ilw a u k e e ,
W I).
R u H ( N O ) ( P P h 3 ) 3 , 132 R u D (N O )(P P h 3 )3 , 133 R u (NO)2 (P P I13 )$ ,* 3 4
RuCl2 (P P h 3)3 *35 and Co(DMG)2 (NO) 97 w e re p rep ared
using lite ra tu re
procedures. The 3 1p{ 1h ), *H and *3c(*H} NMR sp ectra w ere reco rd ed on
a Bruker AM-250-FT NMR spectrom eter operating at 101.256 MHz, 250.133
MHz and 62.896 MHz, respectively. The 3 1p{ 1H) ,*H and 13 c{ 1H) spectra
a re re fe re n c e d to 85% H3 P 0 4 , te tr a m e th y ls ila n e
resp ectiv ely .
(TMS) an d
TMS
In fra re d sp ectra w e re reco rd ed on a P erk in -E lm er 283B
gratin g sp ectro m eter.
The sam ples w ere p re p a re d as e ith e r Nujol mulls
b e tw e e n KBr plates or as KBr pellets, or in som e p ro p er solvent b etw een
NaCl p lates and th e sp ectra are referen ced to th e sh arp 1601 cm" * peak
of a p o ly s ty re n e film .
C onductance m e a su re m e n ts w e re m ad e on
a p p ro x im ate ly 10"3 M n itro b en zen e or su itab le so lv en t solutions using a
34
35
Fisher Scientific P roducts Co. cell (constant= 0.101) and on an In d u stria l
In stru m e n ts co n ductivity bridge Model RC 16B2 o p eratin g at 1000 c.p.s..
Mass sp ectra w ere collected b y Dr. David Chang on VG 7 0 -2 5 0 S double
fo cu ssin g m ass s p e c tro m e te r using FAB (F ast A tom B o m b a rd m en t)
m ethod. Some mass spectroscopy sam ples w ere p re p a re d in th e d ry box
w ith oxygen- and w a te r-fre e solvents ( " 0.5 ml) in th e vial capped w ith
a r u b b e r s to p p e r. E lem en tal an aly se s w e re p e rfo rm e d b y M-H-W
L a b o r a to r ie s ,
P h o en ix ,
Az.
or
O n eid a
R e s e a rc h
S e rv ic e s,
Inc.,
W h itesb o ro , N.Y. C om puter sim u latio n s of e x p e rim e n ta l s p e c tra w e re
p erfo rm ed on DNMR3 program . 136
S y n th e s is
1.
and
R e a c tio n s
o f R uH (N O H C yttp)
S y n th e s is
A solution containing 8.80g (9.58 m m ole) of RuH(NO)(PPh3)3 and 6.20g
(10.6 mm ole) of Cyttp in 70 ml of benzene w as refluxed for 30 min. After
cooling dow n to room te m p e ra tu re , th e so lv e n t w as re m o v e d u n d er
red u ce d p re s s u re to ca,. 1 ml, and 20 ml of aceto n e w as ad d ed
p re c ip ita te th e d ark yellow b ro w n pow der.
to
The solid w as collected by
filtra tio n and w ash ed w ith 5 ml of acetone th re e tim es and d ried u nder
v acuum o v ern ig h t. Yield:
4.90g (71%)
A nal. Calcd for C36H62NOP3RU: C, 60.15: H, 8.69; N, 1.95
Found: C, 60.22; H, 8.42; N, 1.86
2.
R u D (N O )(C y ttp )
36
This co m p o u n d w as p re p a re d
b y th e
p ro c e d u re g iv e n ab o v e fo r
RuH(NO)(Cyttp) using 3.74g of RuD(NO)(PPh3)3(4.07 m m ole) and 3.25 g
of Cyttp (4.46 mmole) Yield: 1.97 g (67.2%)
. R e a c tio n s
a.
W ith
1)
W ith
A c e ty le n e s
P h e n y la c e ty le n e ;
R u (C C P h )(N O )(C y ttp )
RuH(NO)(Cyttp)(200 mg, 0.28 mm ole) w as dissolved in 5 ml of benzene
and 0.50 ml of phenylacetylene (4.6 mm ole) w as added. The solution w as
s tirre d fo r 3 hr. (color changes to d ark g re e n b ro w n ) and th e so lv en t
w as rem o v ed u n d er red uced p ressu re and 5 ml of acetone w as added to
p re c ip ita te o u t th e g re e n p o w d er.
T he p o w d er w as co llected by
filtra tio n and w ash ed w ith 2 ml of acetone th re e tim es and d ried u nder
vacu u m o v ern ig h t. Yield: 140mg (62 %)
M ass Spec.(FAB): p a re n t m /e, 820, th eo ry , 819
A nal. Calcd. for C4 4 H66NOP3RU: C, 64.53: H, 8.12; N, 1.71
Found: C, 63.50; H, 7.96; N. 1.51
Calcd. for Ru(CCPh)(NO)(Cyttp) + 0 : C, 63.29; H, 7.97; N, 1.68
* This com plex is very, air-se n sitiv e and satisfac to ry e lem en tal analysis
d ata could n o t be obtained by com m ercial analytical com pany.
* Mass Spec.(FAB, plain solvent): p a re n t m /e , 834 (Ru(CCPh)(NO)(Cyttp)
+ 0 ), theory, 835
2 ) W ith
1 -o c ty n e ;
Ru(CC(CH2 ) 5 CH3 ) ( N O ) ( C y tt p )
37
RuH(NO)(Cyttp)(200 mg, 0.28 mm ole) w as dissolved in 5 ml of benzene
and 1.0 ml of 1-octyne (6.8 mm ole) w as added. The solution w as stirred
fo r ca. 12 h r. and th e so lvent w as com pletely rem o v ed u n d e r reduced
p re ssu re .
The hig h so lu b ility of th is com pound in com m on organic
so lv en t p re v e n te d isolation.
3 ) W ith
3 - B u ty n - 2 - o n e
a) 1:1 ratio: 2 isom er of Ru(C(CH2 )C(0 )Me)(N0 )(Cyttp)
RuH(NO)(Cyttp) (350 mg, 0.49 mm ole w as dissolved in 5 ml of benzene
and 1.4 ml of 3 -b u ty n -2 -o n e stock solution (0.36 M in bz; 0.50 mmole) was
ad d ed .
(Color changes to d ark g reen im m ed iately ).
The solution w as
stirred for 10 min. and th e solvent w as rem oved under reduced p ressu re
and 5 ml of n-h ex an e w as added to p recip itate out th e brow n solid. The
solid w as collected by filtratio n and w ashed w ith 2 ml of n -h ex an e th re e
tim es and dried u n d er vacuum overnight.
Y ield: 270 mg (71 %)
M ass Spec.(FAB): p a re n t m /e. 786, th eo ry , 787
T h i s com plex is v e r y a ir-se n sitiv e and satisfac to ry e lem en tal analysis
d a ta could n o t be obtained by com m ercial analytical com pany.
b ) T r e a tm e n t w ith
CHCI3 ; [RuC1(C(CH2 )C O M e )(N O )(C y ttp )]C 1
The above product (200 mg) w as dissolved in 10 ml of CHCI3 and stirred
fo r 30 min.
A fter ev ap o ratin g so lv en t u n d er red u ced p ressu re, 5 ml of
n -h e x a n e w as ad d ed and light b ro w n solid w as collected b y filtra tio n
38
and w ashed w ith 2 ml of n -h ex an e th re e tim es and dried u n d er vacuum
o vernight. Yield: 140 mg(61 %) Am =29 c m ^ / Q m o l
A nal. Calc, for C40H66CI2NO2P3RU: C. 58.10; H. 8.04; N, 1.69; Cl, 8.58
Found: C, 56.57; H, 7.32; N, 1.56; Cl, 10.26
Calc, for [Ru(C(CH2)COMe)Cl(NO)(Cyttp))C10.2 CHCI3
C, 56.75; H. 7.84; N, 1.65; Cl, 10.83
NMR (CD2 CI2 ) : in teg ratio n , 8 7.33 (CHCI3 .1 H) / 87.07 (=CH2, tran s,
1H) = 0.29
c)
E xcess
3 - B u ty n - 2 - o n e ;
R u (C = C -C (0 )M e )(N O )(C y ttp )
RuH(NO)(Cyttp)(200 mg, 0.28 m m oie) w as dissolved in 5 ml of benzene
and 5.0 ml of 3 -b u ty n -2 -o n e stock so lu tio n (0.36M in b en zen e; 1.8
m m ole) w as ad d ed (color changes to d ark g reen im m ed iately ).
The
solution w as stirre d fo r 30 min. and th e so lv en t w as rem o v ed u n d er
reduced p ressu re and 5 ml of n-h ex an e w as added. Dark brow n solid w as
collected by filtra tio n and w ash ed w ith 2 ml of n -h ex an e th re e tim es
and d ried u n d er v acuum ov ern ig h t.
C ontam ination of Cyttp oxide w as
found all th e tim e. Yield: 150 mg (69 %)
M ass Spec. (FAB) : p a re n t m /e, 785, th eo ry , 786
"This com plex is v e ry a ir-sen sitiv e and satisfac to ry elem en tal analysis
d ata could n o t be obtained by com m ercial analytical com pany.
4 ) W ith
e t h y lp r o p io la te ;
Ru(C(CH2 )C0 2 E t) (N 0 ) ( C y t t t p )
A solution containing 200 mg of RuH(NO)(Cyttp)(0.278 m m ole) and 0.70
ml of stock solution of eth y l propionate (0.42 M in benzene; 0.29 mmole)
39
in 5 ml of b enzene w as stirred fo r 30 min. (Color changes to dark green
im m ed iately .)
A fter ev ap o ratin g th e so lvent u n d er red u ced p ressu re, 10
ml of m ethanol w as added to p recip itate g reen com pound out. This solid
w as collected b y filtratio n and w ash ed w ith 3 ml of m ethanol th re e tim es
and d ried u n d er vacuum overnight.
Y ield:
180 mg (79 %)
M aas Spec.(FA B) : p a re n t m /e, 817, th eo ry , 817
A nal. Calcd for C41H6 8NO3P 3RU: C, 60.28; H, 8.27; N, 1.71
Found; C, 57.54; H, 7.84; N, 1.26
Calcd. for Ru(C(CH2)C02Et)(N0)(Cyttp) + 0 2: C, 58.01, H, 8.07, N, 1.65
* This com plex is v e ry a ir-sen sitiv e and satisfac to ry e lem en tal analysis
d a ta could n o t be o b tained b y com m ercial analytical com pany.
*
M ass
sp ec.(F A B ,
p la in
s o lv e n t ) :
p a re n t
m /e ,
752
(
Ru(C(CH2 )C02Et)(N0)(Cyttp) + 0 2 ), th eo ry , 749
5 ) W ith
D i m e t h y l a c e t y l e n e d i c a r b o x y l a te ;
Ru(C(C0 2 M e)C (H )C 0 2 M e ) ( N O ) ( C y ttp )
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mm ole) and 0.50 ml
of d im eth y l-acety len ed icarb o x y late (4.1 m m ole) in 5 ml of benzene w as
s tirre d for 30 min (solution tu rn s to d a rk g reen im m ed iately ).
A fter
rem oving th e solvent un d er reduced p ressu re, 5 ml of acetone w as added
and green solid w as collected by filtratio n . This solid w as w ash ed w ith 2
ml of acetone and dried u n d er vacuum ov ern ig h t. Y ield: 180 mg(81 %)
Anal.Calcd.for C42H68N°5P3RU: C, 58.59; H, 7.96; N.1.63
Found: C, 57.84; H, 7.60; N, 1.50
40
6 ) W ith P r o p a r g y l
alcohol; Ru(C=CCH2 0 H ) ( N O ) ( C y t t p )
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 0.40 ml
of stock solution of P ropargyl alcohol (0.68 M in benzene; 0.27 mmole)
in 5 ml of b enzene w as stirred for 4 hr. (color changes to d a rk green).
After ev apo rating the solvent, 5 ml of acetone was added to precipitate
ou t th e g reen pow der. The solid w as collected by filtration and w ashed
w ith 2 ml of acetone th re e tim es and dried un d er v acu u m overnight.
Yield: 130mg (61 %)
M ass Spec.(FAB) : p aren t m /e, 774, theory, 773
Anal. Calcd. for C39 H64NO2P 3RU: C, 60.60; H, 8.35; N, 1.81
Found: C, 58.60; H, 7.74; N, 1.36
Calcd. for Ru(CCCH2OH)(NO)(Cyttp) + 0 2 : C, 58.20, H, 8.01, N, 1.74
* This complex is v e r y air-sen sitiv e and satisfactory e lem en tal analysis
data could not be obtained b y commercial analytical company.
*
M ass
S p e c .(F A B ,
p la in
so lv e n t):
p arent
m /e,
788
(Ru(CCCH20H)(N0)(Cyttp) + 0) , theory, 789
7)
W i th
p ro pargyl
ch lo rid e;
R uC l(N O )(C yttp)
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 0.55 ml
of stock solution of propargyl chloride (0.54 M in benzene; 0.30 mmole)
in 5 ml of benzene w as stirred for 1 hr. (color changes to d ark yellow).
A fter rem oving all solvent, 5 ml of acetone w as ad ded and yellow solid
w as p recipitated out.
The solid w as collected by filtratio n and w ashed
out w ith 2 ml of acetone th re e times and dried un d er vacuum overnight.
Yield: 140 mg (67%)
41
b.
C0 2 - l i k e
1) CS2:
m o le c u le s
R u (S C (H )S )(N O )(C y ttp )
RuH(NO)(Cyttp)(200 mg, 0.28 mmole) w as dissolved in 5 ml of benzene
an d
10-fold excess CS2 w as ad d ed .
Red b ro w n solid w a s fo rm ed
im m ed iately and the solid was collected b y filtration and w ash ed w ith 2
ml of acetone th ree times and dried u nder vacuu m overnight.
Yield: 190 mg (8 6 %)
Anal. Calcd for C3 7 H62NOP3 RUS2 : C, 55.90; H, 7.86; N, 1.76
Found: C, 55.82; H, 7.88; N, 1.70
2)
PhNCO:
R u (O C (H )N (P h ))(N O )(C y ttp )
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 0.80 ml
of stock solution of phenylisocyanate (0.37M in benzene; 0.29 mmole) in
5 ml of benzene w as stirred for 3 hrs. After rem oval of the solvent, 5 ml
of acetone w as added and green solid was precipitated out. The solid was
collected b y filtration and w ashed w ith 2 ml of acetone th r e e tim es and
dried u n d er vacuum overnight. Yield: 160 mg (69 %)
Anal. Calcd. for C4 3 H67N2O2 P3RU: C, 61.63; H, 8.06; N, 3.34
Found: C, 61.67; H, 7.98; N, 3.13
3 ) PhNCS:
R u (S C (H )N (P h ))(N O )(C y ttp )
42
A solution containing 200 mg of RuH(NO)(Cyttp)(0.278 mmoie) and 0.85
ml of stock solution of ph en ylisothiocyanate (0.33 M in benzene; 0.28
mmole) in 5 ml of benzene was stirred for ca. 12 hrs.
After rem oval of
the solvent, 5 ml of acetone was added and g reen solid w as precipitated
out.
The solid w as collected by filtra tio n and w a s h e d w ith 2 ml of
acetone th re e times and dried un der vacuum overnight.
Yield: 120 mg (51 %)
M ass Spec.(FAB) : p a re n t m /e - (SC(H)NPh), 718
‘ This complex is v e r y air-sen sitive and satisfactory ele m e n ta l analysis
data could not be obtained b y commercial analytical company.
4) C02
No reaction w as detected in the 31p NMR spectra from e ith er bubbling
CC>2 for 30 m i n o r adding ch un k of d ry i c e ( l 50 mg) to th e b enzene
solution containing 200 mg of RuH(NO)(Cyttp).
c. O x id a tiv e
a d d itio n
reac tio n
1) 12; [R u l2 ( N 0 ) ( C y t t p ) ] I
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 2.0 ml
of stock solution of iodine (0.14 M in Benzene, 0.29 mmole) in 5 ml of
benzene w as stirred for 30 min. (red brow n solid cam e out im mediately).
The solid w as collected by filtration and w ash ed w ith 3 ml of benzene
th r e e tim es and dried un d er vacuum overnight.
Yield: 150 mg (49 %) am =22.0 cm ^/Q -m ol.
43
W hen ca. 3-fold excess iodine was added, yield w e n t up to 72%.
Anal. Calcd. for C36H6 1 I 3NOP3RU: C, 39.36; H, 5.60; N, 1.27; I, 34.65
Found: C, 38.90; H, 5.42; N, 1.19; I, 34.52
2 ) B r 2 ; [RuBr2 (N 0 ) ( C y t t p ) ] B r 3
The solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 0.40
ml of stock solution of brom ine (0.78M in benzene, 0.31 mmole) in 5 ml
of benzene w as stirred for 30 min. (yellow solid cam e out im mediately).
The yellow solid w as collected b y filtratio n and w a sh e d w ith 3 ml of
benzene th re e times and dried un d er vacuum overnight.
Yield: 140 mg (53 %) a m ° 25.0 cm2/£2 mol
M ass Spec.(FAB) : p a re n t m /e - Br3 , 878, p aren t m /e -Br^, 797,
parent m /e - Brs, 718
Anal. Calcd. for C36 H6 iB r5NOP3Ru: C, 38.70; H, 5.50; N, 1.25; Br, 35.75
Found: C, 38.36; H, 5.33; N, 1.15; Br, 34.88
3) CH3 I;
R uI(N O M C yttp)
A solution containing 150 mg of RuH(NO)(Cyttp)(0.21 mmole) and 0.50 ml
of iodom ethane (8.0 mmole) in 10 ml of benzene w as refluxed for 30 min.
A fter cooling down, the solvent w as ev aporated u n d er reduced p ressu re
and 10 ml of m ethanol was added to precipitate th e green solid out. The
solid w as collected b y filtration and w ashed w ith 3 ml of m ethanol three
tim es and dried u nd er vacuum overnight.
Yield: 110 mg (62 %)
A nal Calcd. for C36H6 1INOP3RU: C, 51.18; H, 7.28, N, 1.66; I, 15.02
44
Found: C, 50.79; H, 7.31; N. 1.58; I, 15.16
4) CH2 I 2 ; R u I(N O )(C y ttp )
This reaction w as conducted by the procedure given above using 100mg
of RuH(NO)(Cyttp)(0.14 m m ole) and 0.50 ml of d iio d o m e th a n e (1.2
mmole).
5)
Yield: 80 mg (68 %)
Benzyl
ch lo rid e:
R uC l(N O )(C yttp)
A solution containing 100 mg of RuH(NO)(Cyttp)(0.14 mmole) and 0.50 ml
of benzyl chloride (4.3 mmole) w as stirred for ca. 12 hr..
Formation of
RuCl(NO)(Cyttp) w a s c o n firm e d b y 3 1p NMR b u t reac tio n w as not
com pleted at th a t tim e and f u r th e r monitoring and isolation of product
w e r e not carried out.
6 ) HC1; R uC l(N O )(C yttp)
A solution containing lOOmg of RuH(NO)(Cyttp)(0.14 mmole) and 0.30 ml
of stock solution (0.49 M in w ater; 0.15 mmole) in 5 ml of benzene was
stirred for 3 hr s. After rem oving all solvents, 10 ml of acetone w as added
to precipitate the yellow solid out.
The solid w as collected b y filtration
and w ashed w ith 2 ml of acetone th re e tim es and dried u n d er vacuum
ov ernight. Yield: 80 mg (76 %)
7 ) HBr
45
a)
1:1
ratio ;
R uB r(N O )(C yttp)
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 0.80 ml
of stock solution of HBr(0.35 M in w ater, 0.29 mmole) in 5 ml of benzene
w as s tir re d for 3 hrs..
A fter re m o v in g all solven ts u n d e r red u ce d
pressure, 10 ml of acetone w as added to precipitate the g reen solid out.
The solid w as collected b y filtratio n and w a sh e d w ith 2 ml of acetone
th re e tim es and dried un der vacuum overnight. Yield: 150 mg(68 %)
Anal. Calcd for C3 6 H6 lBrNOP3Ru: C, 54.20; H, 7.71; N, 1.76; Br, 10.02
Found: C, 53.58; H, 7.35; N, 1.49; Br, 10.38
b ) Excess HBr; [RuBr2 ( N O ) ( C y t t p ) ] B r
8 ) NOBF4 ; [Ru(NO)2 ( C y t t p ) ] ( B F 4 ) 2
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 50 mg
of NOBF4(0.43 mmole) in 5 ml of CH2 CI2 w a s cooled d ow n in liquid
n itro g e n b a th and w a rm e d up slowly to room te m p e r a t u r e (bubbling
w as o b serv ed and color changes to yellow b ro w n) and the solution was
filtered to rem ove u nreacted NOBF4 . The solvent of the filtered solution
w as rem o v e d un d er red u ce d p ressu re and 10 ml of e th e r w as added to
precipitate the yellow solid out. The solid w as collected by filtration and
w a s h e d w ith 3 ml of e t h e r th r e e tim e s a n d d rie d u n d e r v acu u m
o v ern ig h t.
Yield: 160 mg (63 %) Am=54 cm 2 /fi-m o l
Anal. Calcd for C36H6 lB 2FsN20 2 P3Ru: C, 46.92; H, 6.67; N, 3.04
Found: C, 46.70; H, 6.78; N, 2.86
46
9)
Benzoyl
a)
1:1
ch lo rid e
r a t i o ; RuCl(N O )(Cyttp)
A solution containing 140 mg (0.20 mmole) of RuH(NO)(Cyttp) and 0.55
ml of stock solution of benzoyl chloride (0.38M in benzene, 0.21 mmole)
w as s tirre d o v e rn ig h t (color changed to d a rk yellow g re e n gradually).
A fter rem ov ing so lven t u n d e r red u ce d p ressu re, 6 ml of acetone w as
ad ded (yellow solid was precipitated out).
The solid w as collected by
filtratio n and w ashed w ith 3 ml of acetone th re e tim es and dried un d er
v acu u m overnight.
Yield: 120 mg (82 %)
b ) E x cess B e n z o y l C h lo rid e: [RuCl2 ( N O ) ( C y t t p ) ] C l
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 0.50 ml
of b en zoyl chloride (4.3 mm ole) w a s s tirre d o v e rn ig h t ( orange solid
cam e out ). The solid was collected b y filtration and w ash ed w ith 3 ml of
benzene th r e e times and d ried u nder vacuum overnight.
Yield 190 mg (83 %)
Anal. Calcd for C36 H61 CI3NOP3RU: C, 52.46; H, 7.46; N, 1.70; Cl, 12.90
Found: C, 53.07; H, 7.12; N, 1.89; Cl, 13.45
10) CH3 COOH; R u (0 C(0 )CH3 ) ( N 0 ) ( C y t t p )
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 0.40 ml
of stock solution (0.70M in benzene: 0.28 mmole) in 4 ml of benzene w as
47
stirred o v ern ig h t (color changes to dark yellow brow n).
After rem oval
of solvents u n d e r re d u c e d p re s s u re , 5 ml of acetone w a s add ed to
p re c ip ita te th e yellow (other case, green) solid out.
The solid w as
collected b y filtration and w ashed w ith 3 ml of acetone th re e times and
dried un d er vacuum overnight. Yield: 180 mg (83 %)
Anal. Calcd for C3 8 H64NO3P3RU: C, 58.75: H, 8.30; N, 1.80
Found: C, 58.49; H, 8.46; N, 1.64
11)
B e n z o ic
acid ;
R u ( 0 C ( 0 ) ) P h ( N 0 ) ( C y ttp )
A solution containing 200 mg of RuH(NO)(Cyttp)(0.28 mmole) and 40 mg
of benzoic acid (0.33 mmole) in 5 ml of benzene w a s stirred o vernight
(color chang es to d a rk g r e e n yellow ).
A fter rem o v in g all solvents
u n der reduced pressu re, 10 ml of acetone w as added to precipitate
the
green solid out. The solid w as collected by filtration and w ash ed w ith 3
ml of acetone th re e tim es and dried under vacuum overnight.
Yield: 160 mg(69%)
Mass Spec.(FAB) : p a re n t m /e - PhCOO , 7 1 8
Anal. Calcd for C43H66NO3P3RU: C, 61.56; H, 7.93; N, 1.67
Found: C, 60.32, H, 7.29; N, 1.22
Calcd. for Ru(0C(0)Ph)(N0)(Cyttp) + 0 : C, 60.41; H, 7.78; N, 1.64
‘This complex is v e r y air-sen sitiv e and satisfactory ele m e n ta l analysis
data could n ot be obtained by commercial analytical company.
12)
p -n itro p h e n o l;
Ru(0PhNC>2 M N O H C y ttp )
48
A solution containing 180 mg of RuH(NO)(Cyttp)(0.25 mmole) and 0.90 ml
of stock solution (0.28M in acetone; 0.25 mmole) w as stirred for 10 min..
The orange brow n solid form ed im m ediately upon adding p-nitrophenol
solution w as collected b y filtratio n and w a s h e d w ith 2 ml of acetone
th re e tim es and dried u n d er vacuum overnight.
Yield: 180 mg (84 %)
Anal. Calcd. for C42H65N2 O4P3RU: C, 58.93; H. 7.65; N, 3.27
Found: C. 58.98; N, 7.59; N, 3.10
13) O th e rs
R eactions
betw een
RuH(NO)(Cyttp) an d
c y c lo p ro p y l
b r o m id e
and
phenyliodide produce RuBr(NO)(Cyttp) and RuI(NO)(Cyttp), respectiv ely
bu t reaction rates are v e r y slow at room te m p eratu re. The n a tu re of the
products w as inferred by 3 1 p NMR of the sam ples during th e reaction,
and no f u r th e r efforts to isolate the products w e re made.
d.
O th e r
R e a c tio n s
1)
SO2 ; R u ( S 0 3 H )(N 0 ) ( C y t t p )
S ulfur dioxide w as b u b b le d
th r o u g h 5 ml of a b e n z e n e
solution
co ntaining 200 mg of RuH(NO)(Cyttp)(0.28 m m ole) for 5 m in w hile
stirring vigorously.
Color changes to red p u rp le im m ed iately and green
yellow solid w as precipitated out.
The solid w as collected by filtration
and w ashed w ith 3 ml of acetone th re e tim es and dried u n d er vacuum
overnight.
Yield: 180 mg (81 %)
49
Anal. Calcd for C3 6 H62NO4P 3RUS: C, 54.12; H, 7.82 ; N, 1.75; S, 4.01
Found: C, 54.26; H, 7.64 ; N, 1.69; S. 3.88
2)
N -m e th y l-N -n itro so -p -to lu e n e
su lfo n a m id e
(D ia z a ld )
S everal trials u n d e r d iffere n t conditions (tem p, room te m p , or reflux;
so lv en t,
benzene,
e th a n o l or
acetone;
re a c tio n
tim e,
30
m in
or
o v e rn ig h t) to sy n th esiz e Ru(NO)2 (Cyttp) failed. Complicated products
resu lted in e v e ry case.
3) Co(DMG)2 (NO)
NO tra n s fe r reactio n to p re p a re Ru(N0 )2 (Cyttp) b y using Co(DMG)2 (NO)
failed, too. Complicated product resulted.
C S y n th e s is a n d R e a c tio n s o f [RuH2 ( N O ) ( C y t t p ) l B F 4
1.
S y n th e sis
RuH(NO)(Cyttp)(350 mg, 0.49 mmole) w as su spended in 10 ml of eth er
u n d er h y d ro g en -atm o sp h ere and the solution w as cooled dow n to -78°C
( d r y ic e/iso p ro p y l alcohol bath) and excess HBF4 -Et20 w as added.
solution w as w a r m e d up slowly w hile stirring.
changed from d a rk b ro w n to light brown.
The
The color of th e solid
After stirring th e solution
for 15 min. (color changes to dark green brow n), th e solid w as collected
b y filtratio n and dried b y passing h y d ro g en gas th ro u g h th e f r it for 2
days. Yield: 230 mg (43 %)*
50
Anal. Calcd. for C36H6 3 BF4NOP3 RU: C. 53.60; H, 7.87; N, 1.74
Found: C, 47.15; H. 7.12; N, 1.49
Low yield and poor e le m e n ta l analysis re s u lts seem s to be due to
incorporation of HBF4 -Et20 because the product is sticky.
Calcd. for [RuH2 (NO)(Cyttp)]BF4 -1.8 HBF4 'Et2 0 : C. 47.25; H. 7.60; N, 1.28
*H NMR (CD2CI2 ) : integration. 8 7.56- 7.74 (Ph. 5H) / 8 3.45 (OCH2 , 2 H)
= 1.16 ( equivalent to 2.2 HBF4-Et20 )
. R e a c tio n s
a. W ith N e u t r a l L i g a n d 9
1) D2 : [Ru(D2 ) ( N O ) ( C y tt p ) ] B F 4
This reaction w as m onitored by the
3 1p( 1h).
and 2H NMR spectra.
The sample w as made b y dissolving 20 mg of [RuH2 (N0 )(Cyttp)]BF4 in 0.5
ml of CD2CI2 ; D2 gas w as bubbled through th e solution for 3 min..
2) P M e 3 : [R u (P M e3 ) ( N O ) ( C y ttp ) ] B F 4
[RuH2 (N0 )(Cyttp)]BF4-1.8HBF4 -Et20 (150 mg, 0.14 mmole) w as dissolved in
5 ml of CH2 CI2 and 0.15 ml of trim eth y l phosphine (1.00M in THF; 0.15
mmole) w a s added quickly.
Bubbling w as o b serv ed upon addition of
P M e 3 and th e solution w as stirred for 5 min.
No m ore bu bbling was
observ ed and after rem oving solvent un d er red u ce d p ressure, 10 ml of
e th e r w as added to p recipitate the pale yellow solid out.
th e solid was
51
collected b y filtratio n and w a sh e d w ith 3 ml of e th e r t h r e e tim es and
dried u n d er vacu um overnight.
Yield: 110 mg (91 %) AM(acetone)= 146 cm2/£2 mol
Anal. Calcd. for RUP4C3 9 H7 0 NOBF4 : C, 53.18; H. 8.01; N, 1.59
Found: C. 47.22; H, 7.59; N. 1.17
Calcd. for [Ru(PMe3 )(NO)(Cyttp)]BF4 -1.5 HBF4 -Et2 0 ;
C. 48.10; H. 7.62; N, 1.25
3) CH3 CN: [Ru(NCCH3 )(N 0 ) ( C y t t p ) l B F 4
150 mg of RuH(NO)(Cyttp)(0.209 mmole) w as suspended in 5 ml of CH3CN
and th e solution w as cooled d ow n in liquid n itro g e n b a th .
HBF4 Et20 w as added and the solution w as slowly w a rm e d up.
Excess
Bubbling
w as o b s e rv e d and th e so lven t w as rem o v e d u n d e r r e d u c e d p r e s s u r e
quickly.
10 ml of e th e r w as added to precipitate a yellow solid out. The
solid w as collected by filtration and w ashed w ith 3 ml of e th e r and dried
un d er v acu u m overnight.
Yield: 120 mg
* Two products resu lted and several tries to separate them failed.
4) S02
RuH(NO)(Cyttp)( 150 mg, 0.21 mmole) was dissolved in 5 ml of CH2CI2 and
the solution w as cooled down to 77K (liquid N2 ) and excess HBF4 Et20 was
added and th e solution was slowly w arm ed up to room temp.. SO2 gas was
bub bled th ro u g h the solution for 3 min.
After rem oving solvent. 10 ml
of e th e r w as added to precipitate the orange solid out.
The solid was
52
collected b y filtratio n and w ash ed w ith 3 ml of e th e r th r e e tim es and
dried o vernigh t u n d er vacuum . Yield:110 mg
*This reaction also p rod uced tw o p rod ucts and fa ilu re of sep aratio n
p re v e n te d full characterization.
5)
CO;
[Ru(C0 )(N0 )(C y ttp )]B F 4
RuH(NO)(Cyttp)(150 mg, 0.21 mmole) was dissolved in 5 ml of CH2CI2 , the
solution w as cooled down to 77K, excess HBF4 -Et2 0 w as added, and the
solution w as slow ly w a rm e d up to room tem p.
CO gas w as bubb led
throug h th e solution for 10 min. After rem oving solvent, 10 ml of ether
was added to precipitate the pale yellow solid out. The solid w as collected
b y filtra tio n and w a s h e d w ith 3 ml of e t h e r th r e e tim es and dried
overnigh t un d er vacuum .
Yield: 130 mg(64 %)
Anal. Calcd. for C37 H61BF4 NO2 P 3RU: C, 53.37; H, 7.38; N, 1.68
Found: C, 49.83; H, 7.23; N, 1.49
Calcd. for [Ru(CO)(NO)(Cyttp)]BF4-0.9 HBF4 Et2 0 :
C, 49.84; H, 7.21; N, 1.43
6 ) CS2 ; [R u(C S 2 ) ( N O ) ( C y tt p ) ] B F 4
This reaction w as done by th e procedure g iv en above using 0.50 ml of
CS2 (8.3 mmole). A light purple solid w as isolated.
Yield: 120 mg (65 %)
Anal. Calcd. for C3 7 H6 1 BF4NOP3RUS2: C, 50.45; H, 6.98; N, 1.59
Found: C, 49.09; H. 6.8 8 ; N, 1.64
53
b. W ith
A c e ty le n e s .
All products w e re prep ared by using [RuH2 (NO)(Cyttp)]BF4 made in situ
b y th e
p ro c e d u re given abo ve for [Ru(C0 )(N0 )(Cyttp)lBF4 .
Excess
acetylenes and 10 min. reaction time, except for diph eny lacetylen e and
1.4 -d ip h e n y lb u ta d iy n e (1 e q u iv a le n t and o v e rn ig h t ca. 10 h r reaction
time) w e re used and 10 ml of ether w as added to isolate the products and
3 x3 ml of e th e r w as used to w ash followed b y dry in g u n d e r vacuum
o v e r n ig h t .
1)
P h e n y l a c e t y l e n e ; [ R u ( T i2 - C ( H ) C P h ) ( N O ) ( C y t t p ) l B F 4
Red orange solid w as isolated. Yield: 100 mg (53 %)
Anal. Calcd. for C44H67BF4NOP3 RU: C, 58.28; H, 7.45; N, 1.54
Found: C, 57.99; H, 6.96; N, 1.47
2)
D ip h e n y la c e ty le n e ;[ R u ( T i 2 -C 2 H 2 ) ( N O ) ( C y tt p ) ] [ B F 4 l 3
A fter an ov ernight (ca. 10 hr.) reaction, a light yellow solid w as isolated.
Yield: 120 mg (58 %)
Anal.Calcd. for C38 H62B3F i 2NOP3Ru:C, 45.48 ; H, 6.23; N, 1.40
Found: C, 45.27 ; H, 6.52; N, 1.28
S y n th esis
and
1. Synthesis
re ac tio n s
of R u H (N 0 )(ttp )
54
A solution containing 500 mg of RuH(NO)(PPh3 )3 (0.54 mmole) and 5.0 ml
of stock solution of ttp (0.15 M in benzene; 0.74 mmole) in 20 ml of acetone
w as s tirre d for 3 hrs. at room te m p e ra tu re .
A fter re m o v in g solvents
un d er reduced pressure, 15 ml of e th e r w as ad ded and light brow n solid
w as collected b y filtration and w ashed w ith 5 ml of e th e r th r e e times and
dried u n d er vacuum overnight. Yield:
270 mg (71.%)
Anal. Calcd for C36 H38NOP3RU: C, 62.24; H, 5.51; N, 2.02
Found; C, 61.88; H, 5.47; N, 1.86
2.
R e a c tio n s
All reac tio n s including th ose w ith a ce ty le n e (p hen ylacety leneM roo m
te m p e ra tu re ,
CH2 CI2 , ca. 5 -fold excess p h e n y la c e ty le n e , o v e r n ig h t
stirring), CO (room te m p e r a tu r e and 10 min. CO bubb lin g th ro u g h the
CH2CI2 solution)and HBF4 (cool down to 7 7 K and th e n slowly w a rm e d up
to room t e m p e r a t u r e in th e CH2CI2 s o lu tio n .)p ro d u c e d
c o m p lica ted
products. Several tries to separate or purify th e products failed.
S y n th esis
and
R e a c tio n s
of RuH (N O H etp)
1.S y n th e s is
A solution containing 1.80 g of RuH(NO)(PPH3)3(1.96 mmole) and 1.10g of
etp (2.06 mmole) in 30 ml of benzene w as refluxed for 30 min..
After
cooling dow n to room te m p e r a tu r e , all s o lv e n t w a s re m o v e d u n d e r
reduced p ressu re and 20 ml of eth er was added. Light red b ro w n solid was
55
collected b y filtration, w ashed w ith 5 ml of e th e r th r e e tim es and dried
un d er vacuum overnight. Yield: 0.90 g (69 %)
Anal. Calcd for C34H3 4 NOP3 RU: C, 61.17; H, 5.28; N, 2.10
Found: C, 61.03; H, 5.08; N, 2.00
2.
R u D ( N 0 )( e tp )
This com pound was prep ared by th e procedure given above using 2.00 g
of RuD(NO)(PPh3)3(2.17 mmole) and 1.20g of etp (2.25 mmole)
Yield: 1.25 g (86 *)
3.
R e a c tio n s
a) W ith
1)
ace ty le n e
D im e th y la c e ty le n e d ic a rb o x y la te :
[Ru(C(C02 M e)C(H )C0 2 M e ) ( N O ) ( e t p ) ]
A solution containing 140 mg of RuH(NOMetp) (0.21 mmole) and excess
dim eth ylacety lenedicarb ox ylate in 10 mi of benzene w as stirred for 10
min.
After rem oving solvents u n d er red uced p ressure, 10 ml of e th e r
w as added. Dark brow n solid was precipitated out, the solid w as collected
b y filtration, w ashed w ith 3 ml of eth e r th r e e tim es, and dried un d er
v a c u u m overn ig ht.
Yield: 120mg(71 %)
Anal. Calcd for C40H40NO5 P3RU: C, 59.41; H, 4.98; N, 1.73
Found: C, 59.58; H, 5.05; N, 1.64
56
2)
3 -B u ty n -2 -o n e ;
[Ru(C(CH2 )C O M e ) (N O ) ( e tp ) ]
A solution containing 300 mg of RuH(NO)(etp)(0.45 mmole) and excess 3b u t y n - 2 - o n e in
10 ml of b e n z e n e w as s tir r e d for 30 min.
After
rem oving solvents u nd er redu ced pressure, 10 ml of e th e r w a s added.
Red oran ge solid w as p recip ita ted ou t and th e solid w as collected by
filtra tio n and w ash ed w ith 3 ml of e th e r th r e e tim es and d ried under
v acu u m overnight.
Yield:
280 mg (85 %)
Anal. Calcd. for C3 8 H38NO2P 3 RU: C.62.12; H, 5.21; N, 1.91
Found: C,61.97; H, 5.02; N, 1.80
3)
E th y lp ro p io la te ;
[Ru(C(CH2 )C0 2 E t ) ( N 0 ) ( e t p ) ]
A solution containing 150 mg of RuH(NO)(etp)(0.23 mmole) and excess
e th y l pro p io n ate in 10 ml of benzene w as reflu x e d fo r 1 hr..
After
cooling dow n to room te m p e r a tu r e , th e s o lv en t w a s re m o v e d un d er
red uced p re ssu re and 10 ml of eth e r w as added.
Red b ro w n solid w as
precipitated out, th e solid w as collected by filtration, w a sh e d w ith 3 ml
of e th e r th re e times, and dried under vacuum overnight.
Yield: 120 mg (70 %)
Anal. Calcd. for C3 9 H40NO3P 3RU: C, 61.25: H, 5.27; N, 1.83
Found: C, 60.56; H, 5.38; N, 1.79
4)
P h e n y la c e ty le n e
57
This reaction is too slow. ( w ith ca. 3 -fold excess p h en y lacety ien e and
even after 30 min. reflux, the reaction w as not com pleted)
However, 3 1 p NMR spectrum shows the same p a tte rn as above.
F S y n th e s is a n d R e a c tio n s of [RuH2 ( N O ) ( e t p ) j B F 4
1. S y n t h e s i s
This com pound is too unstable to isolate or have its form ation monitored
by NMR.
However, th e pu rp le color o b serv ed during th e process of
w arm up is believed to r e p r e s e n t th e title compound.
The existence of
title com pound w as confirm ed b y th e following reactions:
2. R e a c tio n w i t h P M e 3 ; [R u (P M e3 ) ( N O ) ( e t p ) l [ B F 4 l
This com pound was p rep ared by reacting PMe3 w ith [RuH2 (NO)(etp)]BF4
p re p a re d in situ.
c o n f ir m e d
by
A red b ro w n solid w as isolated.
c o m p a r in g
th e
3 1p
NMR s p e c t r a
The p ro d u ct w as
w ith
[ R u ( P M e 3 )(NO)(etp)lCl, w h ic h w a s c ry s ta lliz e d fro m
th e
a u t h e n tic
r e a c tio n
m ixture b e tw e e n [RuH(NO)(etp)l and PM e3 in b en zen e in th e presence
of trace HC1.
G
S y n th esis
and
1. Synthesis
R e a c tio n s of RuCl(NO)(Cyttp)
58
A solution containing 1.40 g (1.46 mmole) of RuCl2 (P P h 3 )3 , 1.00 g (1.46
mm ole) of Ru(NO)2 (P P h 3 )z and 4.00 g of Zn du st in 40 ml of benzene
w e r e refluxed for 30 min.
gray.
Color changed from d a rk b ro w n to g reen
Benzene solution w as tr a n s f e r r e d to a
flask containing 1.95g
(3.33 mmole) of Cyttp w ith filteration via cannula and the color changed
to d ark yellow im m ediately.
A fter rem oving ben ze n e u n d e r red uced
pressure, 20 ml of acetone was added, and dark yellow solid w as collected
via filtration and dried un d er vacuum overnight. Yield: 1.85 g. (85 %)
Anal. Calcd for C3 6 H61CINOP3RU: C, 57.40;H, 8.16; N, 1.86; Cl, 4.71
Found: C, 57.60;H, 7.90; N, 1.77; Cl, 4.96
2.
R e a c tio n s
a.
E lectro p h ilic
1)
P ro to n a tio n
a) HBF4 ;
a tta c k
[R u(N O )C l(C yttp)][B F 4 l 2
A solution containing 150 mg of RuCl(NO)(Cyttp)(0.199 m m ole) and
ex cess
HBF4 -Et2 0 in 5 ml of CH2 CI2 w as s tir re d for 30 min.. A fter
rem oving solvent, 10 ml of e th e r was added to p re cip ita te the yellow
solid.
The solid w as collected b y filtration, w ash ed w ith 3 ml of eth e r
th r e e times, and dried under vacuum overnight.
Yield: 110 mg (66 %)
Anal. Calcd. for C3 6 H61B2CIF8NOP3 RU: C, 47.35: H, 6.73: N, 1.53: CJ, 3.88
Found: C, 46.65: H, 6.67; N, 1.47; Cl, 4.52
59
b)
HC1: [Ru(NO)Cl2 ( C y t t p ) ] C l
This reaction w as m onitored b y 3 1 p NMR. The same product as above
w as confirmed.
c) HBr; [Ru(NO)BrX(Cyttp)l X (X-Cl o r Br)
This
reac tio n
w as
also
m o n i to r e d
by
3 1p
NMR.
I n it ia l ly
[Ru(NO)Cl(Cyttp)]Br was form ed b u t after 1 day, most of it con verted to
[Ru(NO)BrX(Cyttp)lX
b.
A tte m p te d
sy n th e sis
of R u R (N O )(C y ttp )(R -P h ,
Me)
This reaction w as accomplished by using RuCl(NO)(Cyttp) and LiR in THF
for prolonged reaction tim e (up to one day).
No reaction w as detected.
W hen thallium or silver salt w as used to pull o ut the chlorine, a mixture
resulted.
c. W ith n e u t r a l L ig a n d
1). P M e 3 : [ R u ( P M e 3 )( N 0 ) ( C y t t p ) l C l
This reaction w as monitored by 31 p NMR. The product was confirmed by
c o m p a rin g
th e
3 I p NMR s p e c tru m
[ R u ( P M e 3 )(NO)(Cyttp)]Cl.
H o w ever,
w ith
th e
an
a u th e n tic
r e a c tio n
completion ev e n though excess ( 10-fold) PMe3 w as used.
did
sa m p le of
n o t go to
60
H.
S y n t h e s i s o f V in y lid e n e C om plex
[R u (C C (H )P h )(N O )(C y ttp )]B F 4
A solution containing 100 mg of Ru(CCPh)(NO)(Cyttp) (0.12 mmole) in
5 ml of CH2CI2 was cooled down to 77K, an excess of HBF4 was added and
the solution w as w arm ed up slowly. The color of the solution changed to
purple red, the solvent was rem oved un der reduced p ressu re and 10 ml
of e th e r w as added to precipitate the red pu rple solid.
The solid w as
collected b y filtration and w ashed out w ith 3 ml of e th e r th re e times and
dried un der vacuum overnight. Yield: 90 mg (81 %)
Anal. Calcd. for C44H6 7 BF4NOP3 RU: C, 58.28; H, 7.45; N, 1.54
Found: C, 53.13; H, 6.64; N, 1.45
Calcd. for [Ru(CC(H)Ph)(N0 )(Cyttp)BF4 -HBF4 -Et2 0 :
C, 53.94; H, 7.26; N, 1.31
^
NMR (CD2C12 ) : integration, 8 5.84 (=CH(Ph), 1H) / 8 3.43 (OCH2, 2H)
= 0.37 ( equivalent to 1.3 HBF4-Et20 )
CHAPTER IV
S tr u c tu r e s
In
of
this
R uH (N O )P 3 ( P 3 :
section,
discussed.
RESULTS AND DISCUSSION
This
the
C h e la tin g
structural
appears
to
T rip h o s p h in e )
assignments
of
RuH(NO)P3 will be
be important because,
as
seen
in
the
introduction, the reactivity of the nitrosyl complexes is closely related
to
the
structure.
starting
materials
these
compounds.
monophosphine
between
Therefore, understanding
will
help
First
compounds
monophosphine
to explain
of all, the
will
be
and chelating
of
the
and predict
reported
structure
the chemistry
structure
surveyed
and
of
the
of
of analogous
the
difference
triphosphine complexes
will be
discussed.
1.
S tru ctu res
of MH(NO)L-3
(M=Ru,
Os,
Ir,
L=m onophosphine)
Since the first preparation of [IrH(NO)(PPh3 )3 ]X (X=C104,BF4 or PF6) by
Roper et. a l . , m
the structure and bonding mode of NO have drawn
attention because it is found that this compound has three isomers. In
addition, closely related compounds such as [IrX(NO)(CO)(PPh3)2 ][B F 4 ]
(X=C1, I),29 [IrC l2 ( N O )(P P h 3)2 l 8 and [Ir(CH3 )I( N O ) (P P h 3 )2 ] 138 have
square pyramidal
(SP)
structures with bent NO
brown (and/or green) isomer was
61
groups. Initially,
the
assigned to have a SP structure with
62
bent NO group, while the black isomer was thought to have trigonal
bipyramidal
stretching
1720
(TBP) geometry with linear NO group based
frequencies of the NO group
c m 'l ) .
Later, X-ray
on the IR
( black, 1780 c m 'l ;
structure determination
proved
brown,
that both
isomers have linear NO group but at different sites, (see Fig. 6)42a,
Ib ers^a
claimed
that the low electronegativity
and minimum
127
steric
requirement of the hydrido ligand might be the reason for differences
in geometry and NO bonding mode.
Wilson and Osborn^ 8 reported
the
synthesis of a scries of MH(NO)L3 . ( M = Ru, Os ; L = PPh3 ,P P li2 M e ,
P P h 2(i-Pr), PPh2( C 6H u )).
H
” 1+
I ,-P P h 3
Ph3P— . r ^ pph3
PPha 1 +
I
P h a P -.r ^
ND
PPh3
Black Isomer
Figure
6
Brown Isomer
S tru ctures
of Isomers
of
[IrH(NO)(PPh3 )3 ] [ C 10 4 ]
When L is PPh3, structure A in Fig 7 was proposed for the geometry and
structure B was assigned when L is PPh2 Me and at -110°C.
The structural
differences with L was attributed to the difference of steric demand of
L . 1 2 6
These compounds are found to be fluxional, and intramolecular
rearrangement between structure
A and C when
L
is PPh2 (i-Pr)
P P h 2(C 6H n ) was proposed based on the NMR and IR data.
or
E i s e n b e r g l 2 6
63
confirmed
this
proposal
by
X-ray
crystallography
for
the
case
of
RuH (NO )(PPh3)3.
ISD
Ls. 1
— L
L
1
H
O k
Spectroscopic
Data
1
— L
L ^ /%
L
L
C
L
B
A
Fig. 7
ISD
1
H
Proposed
Structures
of MH(NO)L3
of RuH(NO)P3
In contrast to the monophosphine analogues, these compounds do not
show any fluxionality from 210K to 342K except fac-RuH(NO)(ttp) (this
structure and mechanism of fluxionality will be discussed separately).
For Cyttp and mcr-ttp compounds, the peak of the central phosphine
appears upficld from that of the wing phosphincs in 31 p NMR spectra
while reverse pattern is observed for the etp case.
chemical
e f f e c t
shift of the chelating phosphine
8 an(j trans ligand cffect.125
is
(See Table 1.)
influenced
by the
The
ring
in the 6-member ring system, the
trans ligand effect is predominant, while the ring effect is predominant
in
the
5-member
ring.
Therefore,
determining the geometry of the complex.
typical
v a l u e s .
1^5
these
effects
are
useful
in
AR's of RuH(NO)P3 show the
However, since this system has two strong trans
ligands (H and NO), trans ligand effect does not help to assign the
structures for the
Cyttp and ttp cases.
It is well recognized that the d^
complex prefers SP structure while d^ complex favors TBP. 139,
140
Table 1. 31P NMR Parameters of Ruthenium Hydridonitrosyl Complexes.
Aa, p p m
ARb , ppm
Solvent
35.8
55.1
-12.8
benzene-d6
39.8
36.1
-31.8
CD2Q 2
Complex
SP ceter» PPm
SPwing* PPm
2Jpo,
RuH(NO)(Cyttp)
26.99
48.25
7.90
34 .5 2
m er-RuH(NOXttp)
fac-RuH(NO)Cttp)
2 2 .5 2
RuH(NO)(etp)
106.42
RuH(NO(PPh3)3
61.88
[RuH2(NO)(Cyttp)]BF4
_
83.09
18.8
Hz
_
123.0
67.9
8.35
38.65
25.0
CD2CI2
55.1
benzene-dfi
benzene-dfi
CD2 CI2
a. A : 6P center,com plex ~ SP free ligand
b. A r : A com plex _ ^m onophosphine
complex
c. at 303 K
►fc.
I
Table 2. *H NMR and IR Spectral Data of Ruthenium Hydridonitrosyl Complexes
Complex
8H( or 8D ), ppm 2JPH, H
RuH(NO)(Cyttp)
-9.05 (dt)
z
24.9, 7.3
S olvent
v(Ru-H)
v(NO)
m e d iu m
Q>D6
1 80 0
1580
Nujol
M ull
RuD(NO)(Cyttp)
-9.19( broad s )
m er-RuH(N O)(ttp)
-4.37 (td)
fac-RuH(NO)(ttp)a
-4.72(dt, broad) 18.0, 8.1
RuH(NO)(etp)
-3 .1 9 (td )
54.4, 23.4
RuD(NO)(etp)
-3.70(broad, d)
RuH(NO)(PPh3)3c
-6 .3 5 (q )
1 290(1293)h 1 5 9 0
CD2CI2
1885
1608
it
it
1830
1585
tt
C6D6
184 0
1600
tt
5 .4 4
c h 2c i 2
1305(1307)b 1615
tt
3 0 .0
C6D6
1965
48.1, 26.5
-
RuD(NO)(PPh3)3c
[RuH2(NO)(Cyttp)]BF4
«t
CH2C12
-6 .7 3 (b ro ad )
CD2Q 2
1640
(1396X 1 6 6 0
1 9 4 0 ,1 8 5 0
1760
tt
tt
CH2 CI2
a. at 303 K
b. theoretical value
c. reference 131
* IR stretching frequencies are measured in unit of cm-1
CN
I
r
r>1
50
49
J_
48
—J.
(
47
46
t------1------1------1------- (----t------1------1------(------(------(------1------(------(------- 1---- ]------1------1------1------^----45
44
43
42
41
40
39
38
37
36
35
34
33
32
31
30
29
28
27
26
25
PPM
Fig. 8. 31p{lH } NMR Spectrum of R uH (N O )(Cyttp) in C6D6 a t 101.252 MHz
ON
ON
I
Fig. 9. 1H NMR Spectrum of R uH (N O )(Cyttp) in C6D6 a t 250.133MHz
J ^
—1
110
I
I
100
1 |------------- ■ |
106
104
I
1------------- 1--1--------------!-- 1-------- 1------------1---- 1------------ 1--------- 1---1-------- 1----------- 1-----1------------1---- 1------------ 1---- 1-----------1----------- 1-- 1--------1------------1---- 1------------ 1------1----
102
100
06
S6
94
PPX
92
90
aa
86
B4
82
Fig.10. 31p{lH } NMR Spectrum of RuH (N O )(etp) in C6D 6 a t 101.252MHz
80
76
»
IN T E 6 R A L
5 .0
4 .0
3 .0
-.0
-
1.0
-
2.0
-3 .0
PPM
Fig. 11.
NMR Spectrum of RuH(N O)(etp) in CgD6 a t 250.133 MHz
-4 .0
70
T
T
T
T
~T
T
1000
500
OnH
* measured as % transmission.
Fig. 12. IR Spectra of RuH(NO)(Cyttp) and RuD(NO)(Cyttp) in
Nujol Mull
71
r
T
T
T
~r
loco
1500
soo
Cm'1
* measured as % transmission.
Fig. 13. IR Spectra o f RuH(NO)(etp) and RuD(NO)(etp) in
Nujol Mull
72
- 1—
3 6 .0
— I—
3 7 .0
I
I
3 6 .0
3 3 .0
3 1 .0
3 0 .0
PPM
2 9 .0
— I—
2 4 .0
—
n
2 2 .0
; i
Fig. 14. (a)13C { 1H ) NMR Spectrum of R uH (N O )(Cyttp) in C6D 6
a t 62.896 M Hz and (b) NO E S p e c tr u m ( Ir ra d ia te d a t the
h ydride peaks) in C6D<; a t 250.133 MHz
/
— I—
2 1 .0
73
Therefore, it is reasonable to
assign
a SP structure if NO is bent
(formally, bent NO is regarded as NO" and ruthenium is d^), while a TBP
structure is preferred if NO is linear (ruthenium is d^).
no tool
To date, there is
to assign the bonding o f NO unequivocally.
IR
stretching
frequencies of NO's of these complexes are rather low (~ 1600 cm "l)
but
a recent paper *41 reported that vNO
o f w ell-characterized
complexes goes as low as 1427 cm"*-
Therefore, it is not safe to assign
the structure by the IR data only.
^ J p .p
than that of Cyttp or ttp complexes.
linear NO
0f the etp complex is smaller
This phenomenon is typical for the
5-member ring system and has been attributed to different sign of the
coupling
and
constants o f through-metal
M e e k l4 3
Co(I)
coordinate
Ru(O)
are
Dubois
t h r o u g h - b a c k b o n e . 1 4 2
reported that ^ j p p is sensitive to the geometry in 5-
coordinate
regions
and
com plexes.
well
Lim ited
com plexes 144,145
applicable
but
survey
proves
of
that
generalization
isoelectronic
proposed
needs
5-
em pirical
some
caution.
From the experimental values of ^Jpp of Cyttp and mer-ttp complexes, a
SP structure where central phosphine occupies apical site is favorable (
A in Fig 15 ), but a TPB structure, where wing phosphincs occupy the
axial sites( B in Fig 15 ), is still possible.
rrx
r r ..h
P— Ru— P
P— RuL
of
A
F ig.
15
P ossib le
B
S tru ctures
of
R u H (N O )(C yttp)
mer-RuH(NO)(ttp)
and
74
Since
no
bent
NO is found at the basal site of SP geometry, or at the
equatorial site of TBP, linear NO is proposed.
o f RuH(NO)(Cyttp) is
abnormally
low
However, one of the ^ J p jj's
(7.3Hz)
while
those of mer-
RuH(NO)(ttp) fall in the normal range for cis coupling.
explanation
constants
is that
have
One possible
I^ J p - H . transl > l-^Jp-H . cisl and these coupling
the
opposite sign which
is
true
in
most
c a s e s . ^ 4
6
Therefore, if the angle of H-Ru-Pc e n t er is >n the turning point where
the sign of
changes, a small value of ^ Jp -H is possible.
point o f view,
expected
to
geometries
be different,
o f RuH(NO)(Cyttp)
especially
in
angle
though the basic structure might be the same.
and
From this
RuH(NO)(ttp)
of H-Ru-Pc c n tc r
are
even
For the RuH(NO)(ctp), it
is difficult to determine the meaning of 2 j p . j | ( 54.4
Hz) because this
value falls on the border line between trans (usually higher than 80 Hz)
and cis (20~50
Hz) coupling constants.
Since
wing phosphincs
identical in the 31p{lH }N M R spectrum, the following structures
16 ) are all possible.
<
T
p c r ^
\
^Ru— P
r T
"
ND
p
16
of
C
B
A
Fig.
P— Ru.— P
CN^ |
H
Possible
S tru c tu re s
of
R uH (N O )(etp)
(
are
Fig.
75
However, since the formal oxidation state of ruthenium is 0 (only linear
NO is possible for the proposed structures) and d® favors TBP, structure C
(SP) can be eliminated.
one
based
structure
on
the
of
Between A and B, it is difficult to pick the right
spectroscopic
data only.
[R u(PM e 3 )(N O )(etp )]C l
was
Fortunately,
the
crystal
determ ined
by
X-ray
crystallography and this result favors structure B.
TBP
structure,
maximum
tt-acceptor
ligand
favors
the
Furthermore, in the
equatorial
position
for
o v e r la p ^ , and placement of the hydride ligand on the axial
position
can
central
metal
hydrogen
lead to
to
m ove
147
a t o m .
minimum nonbonding repulsions by
out
of
the
Deuterium
equatorial
analogues
plane
of
allowing the
away
RuH(NO)(Cyttp)
RuH(NO)(etp) help to determine th e v R u-H in the IR spectra.
assignment o f
v
r u _ d .
from
the
and
Despite the
their existence is suspicious because these peaks
are not distinctive.
From the l^ C ^ H )
NMR spectra, meridional geometry
was
Recently,
found
confirmed.
cyclohexyl
ring
appears
as
geometry, while it gives a
it
was
a
triplet
that
when
ipso
Cyttp
has
carbon
a
of
the
meridional
doublet o f doublets when Cyttp has a facial
geometry. This phenomenon resembles the virtual coupling o f PMe2 P h
in the
the
NMR spectra, which is useful in determining the geometry of
c o m p l e x e s .
148
However, general application o f this phenomenon
requires caution because an exceptional e a s e l49 was reported.
X -ray
C rystal
Structure
of
RuH (N O )(C yttp)
Ambiguity o f the structure assignment o f RuH(NO)(Cyttp) based on the
spectroscopic
Crystals
were
data
required
grown
from
an
X-ray
crystal
structure
a benzene/ether/acetone
determination.
mixture
under
an
76
argon stream.
Fig.
RuH(NO)(Cyttp).
shows the ORTEP view o f the final structure of
1 7
The structure o f RuH(NO)(Cyttp) is highly distorted
from the ideal TBP, with the central phosphine, nitrosyl and hydride
ligands
com prising
ligands
occupying
intermediate
the
equatorial
the
between
axial
TBP
plane
and
positions.
and SP.
two
It
The
is
wing
best
ruthenium
phosphine
described
atom
is
as
slightly
displaced from the plane which triphosphine comprises toward the NO
ligand
This
( 0 . 3 9 A ) .
structure where two
type
axial
o f displacement
R h H (C O )(P P h 3 ) 3 ; 1 5 0
common
in
the TBP
ligands show different coordinating
RuH (N O )(PPh 3 ) 3 ; 1 2 8
( 0 . 5 5 A ,
is
0 . 5 l A ,
abilities
CoH (N 2 )(P P h 3 >3 ; 150
( 0 . 0 3 0 A ) ,
[IrH(N 0 )(PPh 3 ) 3 ]C 1 0 4
0 . 3 6 A
,
(black isomer)4 2 *).
This displacement is partly responsible for the slight deviation o f the
angle between ligands from the ideal values.
angle
o f P 2 -Ru-N,
orthohydrogen
of
it
the
appears
that
the
phenyl
ring
of
(See Table 3.)
clo se
the
contact
central
between
phosphine
nitrogen docs not cause distortion from the ideal position.
Waals radii;7 5 1 j|,
1 . 1 _ 1 . 3 A ;
N,
H 1 7 ...N,
1 . 5 A ;
c lo s e ly
related
ttp
com plex;
between
orthohydrogen
of
the
and
(Van der
was observed for the
R h(ttp)C l;
9 0 . 7 3 ( 2 ) ° ;
[ R h ( t t p ) ( N O ) C l ] [ P F 6 ] , 2 3 a ) and the reason
Interaction
9 0 °
the
A slight widening of
2 . 9 9 A ) .
the bite angle of Cyttp is observed (approximate
For the
for this
central
9 0 . 3 4 ( 8 ) ° ,
is not clear.
phosphine
phenyl
ring ( H i 7 ) and the hydrogens o f the cyclohexyl ring ( H i C n and H i C n ' )
may
be the reason because the
comparable
with
1 5 3 . 1 ° ,
1 6 1 . 7 ° ,
angle
and
1 4 1 . 6 °
R h H C l(P P h 3 ) 2 (S iC l 3 ) - XSi HCl 3 1 5 3 and
isomer)I2 2 ,
equatorial
where
plane
accommodation
causes
this
of P i - R u - P
type
in
1
’( 1
5 7 . 8 1
( 3 ) ° )
is
RuHCl(PPh 3 ) 3 f 1 5 2
[IrH(NO)(PPh 3 ) 3 ][ClC>4 ] (brown
of
of
bulky
PPI13
deviation.
or SiCl 3 in
A lso,
the
structural
77
U
I# 03
C20
CN)
C_J
u
O)
03
CJ
in
n
•H
u
Fig. 17. X -ray C rystal S tru c tu re of R uH (N O )(C yttp)
to
u
S elected B o n d L e n g th s a n d A ng les o f
R u H ( N O ) ( C y t t p ) __________________
A to m s
A n g le , deg
Ru - Pi
2 .3 2 6 ( 1 )
P 1 -RU-P 2
9 3 .6 1 ( 2 )
2 .2 9 5 ( 1 )
P l-R u -N
9 4 .9 6 ( 3 )
Ru - N
1 .7 8 3 (4 )
P l-R u -P i'
1 5 7 .8 1 ( 3 )
Ru - H
1.62 (5)
P l- R u - H
7 9 .9 ( 1 8 )
N
1 .1 8 6 (5 )
P 2-R u -N
1 3 4 .2 (2 )
P 2-R u -H
8 4 .8 ( 1 8 )
N -Ru-H
1 4 1 .0 ( 1 8 )
c
1
D ista n c e s,A
90
A to m s
hs
to
T a b le 3.
_________
-0
♦standard deviation is shown in the parenthesis.
T a b le
4.
A to m s
C o m p a r is o n o f S elected
of T rip h o sp h in e
R h (ttp )C l
B o n d D is ta n c e s
C o m p le x e s
and
A ngles
[R h (ttp )C l(N O )]P F 6 R u H (N O )(C y ttp )
M -P i
2.2 8 8 (1 )A
2 .3 7 4 (3 )A
2.326(1)A
m -p
2 .2 0 1 ( 2
2 .2 8 2 (4 )
2 .2 9 5 (1 )
2
)
P 2 -C 3
1.827 (4)
1.8 2 9 (1 1 )
1.8 33(3)
P 2 -C 16
1.836 (6)
1 .79 7(9)
1 .849(5)
M -P 2 -C 3
118.1(1)0
116.7(4)o
1 17 .9(l)o
M -P 2- C i ,
112 .5(2)
1 11.9(4)
116.5(2)
98.4(2)
9 8 .7 (5 )
9 8 .6(3 )
C 3 -P 2 -C 3
1. Standard deviation is shown in the parenthesis.
2 . Pi and P 2 represent central and wing phosphines, respectively.
3. C 3 , C 3 1 and C i 6 represent ipso carbons of phenyl or cyclohexyl ring
of wing phosphine and nearest carbon of propyl back-bone to the
wing phosphine, respectively.
79
differences (TPB in this case while ttp complexes have SP or square
planar structure) may play some role in
this deviation.
Moreover, in
these complexes,
where large deviations of P i - R u - P i ’ angles are found,
the positions of
the hydride ligands are not ideal - primarily due to the
proxim ity
phenyl
of a
a - h y d r o g e n . 150
The
angles between the
equatorial bulky ligands and hydride are 89° and 69° in RuHCl(PPh3)3
and
R u H C l( P P h 3 )2 ( S i C l 3 ) -x S i H C 1 3 ,
r e s p e c tiv e ly .
(F or
[IrH (N 0 )(P P h 3 )3][C 1 0 4 ] (brown isomer), the hydride was not located).
In
RuH(NO)(Cyttp), the hydrogens of C9 and C9' (H1C9 —RU, 4.23A; H2C9 "-Ru,
3 .4 6 A)
seem
to
prevent
hydride
ligand
from
occupying
position, and the angle of Pi-R u-H is 79.9° as a result.
the
ideal
The NO ligand is
essentially linear and this result is rather surprising because VNO
the IR spectrum is rather low(1580 cm‘ l ) and increased n-back
might favor a bending o f
{MNO}
group.^0
(Triphosphines
basic than the monophosphine analogues 52,57,154
in this complex is more favorable than
in the
bonding
are
an(j n -back
*n
more
bonding
isoelectronic complex
[ R h C l( N O ) ( C y ttp ) ] [ P F 6 ] where NO is bent. However, recalling that
increased electron density on the metal atom (crucial energy level of
d z 2 also increases) may lead to the bending of the NO group or to the
structural change to the TBP,25 th e structural change process seems to
be energetically
com parable
with
favorable in this
that
case. Ru-N
(1.792(11)A)
in
distance
(1.783(4)A) is
RuH (NO )(PPh3 ) 3 .
It must be
pointed out that Ru-N distance is sensitive to the position of NO group in
TBP structure as found in the isoelectronic iridium complexes; distance
of axial NO (1.68(3)A) is shorter than that o f the equatorial NO in
[IrH (N 0 )(P P H 3)3][C 1 0 4 ].42a,127
Therefore, it is safe to say that a change
of monophosphine to chelating phosphine leads to a shortening of the
80
Ru-N distance as expected primarily owing to increased electron density
on the metal atom in the triphosphine complexes.
distance
does
1.186(5)A ;
not
show
any
significant
RuH(NO)(PPh3 )3 , 1.183(11)A),
the above conclusion.
However, the N -0
elongation
(RuH(NO)(Cyttp),
and this leads one to suspect
As Eisenberg et. a l . ^ 5
indicate, the relatively
large estimated standard deviation in RuH(NO)(PPh3)3 makes it difficult
for comparison with. The observed M-N distance lies in the middle of the
range
reported
for linear NO complexes ( 1.68~ 1.89A), and it is also
comparable with 1.80(4)A in the RuI(NO)(CO)(PPh3)2 ^ ^ case where NO
is fairly bent(159(2)°). The Ru-P distances trans to each other(Ru-Pwjng)
are longer than that which does not have trans phosphine(Ru-Pcenter)
(2.326(1)A
v s.
2.295(1)A as in RuCl2(PPh3)3(2.329A and 2.36A vs 2.206A)
and in [Rh(ttp)(NO)Cl][PF6]-(2.374(3)A vs. 2.282(4)A) Also, Ru-P distances
are shorter than those in other Ru(O) complexes
( RuH(NO)(PPh3 ) 3 1
2.345(3) and 2.328(3)A ; RuI(NO)(CO)(PPh3)2 , 2.391(8)A; Ru(NO)2(PPH 3)2
5C 6H 6 , 2.337(2) and 2.353(2)A 157 ; Ru(CNCMe3)4 (P P h 3 ),158 2.338A ).
M oreover,
d is to r tio n s ^ ^ which are the consequences of shortening the
Ru-P distances, such as longer P-C bonds to the phenyl ring, cyclohexyl
rings and propyl chain, an opening of the Ru-P-C angles and a closing
of the C-P-C angles, are found as in [Rh(ttp)(NO)Cl][PF6 ] and Rh(ttp)Cl;
in this complex, the degree of distortion is more severe.
Relatively low
angle (P2 -Ru-H,
(See Table 4)
(7.3Hz) appears to be primarily due to an unusual
84.8°), although some electronic effect can contribute
to it because mer-RuH(NO)(ttp) shows 7 Jp -H in the normal range.
From
the NOE (Nuclear Overhauser Effect) experiment, it is believed that the
phenyl ring of the center phosphine occurs at the same side of hydride
8 1
ligand which is contrary to the result of the X-ray crystal structure.
H ow ever,
structures
from
as
H o ffm a n n ^ S pointed
o f sim ilar
solution
energy,
structures.
solid
This
out, if there are
state
structures
statem ent
is
many
may
also
be
possible
different
applicable
to
R u H C l(P P h 3 ) 3 1 6 0 t which has identical phosphines in solution but two
different sets of phosphines in the solid state.
S tru c tu re
and
F lu x io n al
M echanism
of
fac-R u H (N O )(ttp )
From the NMR
experiment, fac-RuH(NO)(ttp) is found to show
fluxional
behavior in the
range of 180 to 303 K (Fig. 18 and 19).
order to
elucidate a fluxional mechanism and
In
structure of fac-RuH(NO)(ttp) the
following experimental and simulation data should be considered.
a. mer- and fac-RuH(NO)(ttp) do not interchange (or it is too slow on the
NMR time scale).
b.
No phosphorus
throughout
the
peak
assignable
tem perature
to
dangling phosphine was
found
range.
c. Simulation shows that three isomers are required where two of them
are very similar and the outside two phosphorus peaks interchange.
d. Interchange of the outside two phosphorus peaks shows that signs of
two 2jp_p>s and the other ^ Jp .p are different.
e. One of ^Jp-H (55.0 Hz) indicates that one phosphorus is located trans to
hydride even though it is not too large as in the case of RuH(NO)(etp)
(vide
supra).
Therefore, the following mechanism is proposed(Fig. 20).
303K
i l
i
L
82
.
287K
kuXr^
273K
J j
Aj l
253K
233K
213K
J
i1
j
;J
*i V-M
*w
ca)
a>)
Fig.18. V ariable T e m p e ra tu re
R uH (N O )(ttp)
3 1 P{*H}
-o
—
NMR S p ectra of
in C D 2 C12 at 101.252 MHz (a) E xperim ental
(b)
C a lc u la tio n
303K
rwUl/H
287K
273K
253K
233K
A ^I/'A A '
213K
( b)
Fig.
19. V a r ia b le T e m p e r a t u r e
R u H (N O ) (ttp )
in
■7i
*H N M R S p e c tr a o f
C D 2 C I 2 a t 250.133 M H z (a) E x p e rim e n ta l
(b)
C a l c u l a ti o n
Fig.
20
P roposed
F luxional
M echanism
of
fac-R u H (N O )(ttp )
As mentioned before, the chemical shift of phosphorus peak in the
NMR spectra is sensitive
trans
effect
ligand
to the nature of trans ligand.
pushes
the
chem ical
sh ift
Generally, high
upfield;
quantitative changes by specific ligands are not known.
31 p
how ever,
Since H and CO
show similar trans e ffe c t^ l and NO is stronger rc-acceptor than CO, it is
expected that chemical shift of phosphorus trans to NO appears upfield
relative to that trans to
H which, in turn, is upfield
having
However,
no
rationalize
simulation.
trans
ligand.
the
chem ical
shifts
of
in structure
wing
II,
it is
phosphines
relative to that
difficult to
used
in
the
Inspite of this shortcoming, the following assignments of
^ 1P NMR peaks
simulation data.
are shown in Table 5 based on experimental
and
These assignments are consistent with the trend of ^ j p .
T able 5. 31P N M R
p aram eters
I
3575
II
in
T a b le
2 Jp-PPh,Hz 2 JP-P\Hz
23 11
2939
27.0
22.3
-41.0
3547
231 1
2039
27.0
22.3
-41 .0
2039
231 1
3575
22.3
27.0
F u n c tio n
V a lu e s
of T hree
Exchange
Processes o f fac-R uH (N O )(ttp)
Process
S im u la tio n
8 P’Ph 2 (Hz)
6 .T h e r m o d y n a m ic
(Hz)
fo r
o
8 PPh
1
5PPh2(Hz)
S tru ctu re
o f fa c -R u H (N O )(ttp )
AG*, Kcal/mol.
AH* Kcal/mol.
AS* Cal/mol.K
12
1 2 .2
3.3
-32.6
13
1 2 .8
13.9
3.8
23
1 2 .8
13.9
3.8
2 JP'-PPh,Hz
86
P- (2 J a x ia l- e q u a to r ia l's
have comparable signs and value while 2 J
e q u a to ria l-e q u a to ria l
show
different
Thermodynamic
values
are
the
function
comparable
intram olecular Berry pseudorotation
process
signs
and
absolute
with
those
value)
found
in
processes. 1(>3 However, AS* of
12 is too large for intramolecular rotation and no reasonable
explanation cannot be made. Since TBP is usually more stable than SP,
another mechanism including TPB molecules is possible, but difficulties
in
assignm ents
of
experim ental
and
theoretical
data
(especially,
phosphorus peak assignment) favor the proposed mechanism.
Another
possible mechanism is that which includes SP structures with bent basal
NO groups as low temperature limiting structures. In this mechanism,
there
is
no
problem
in
assigning
the
nmr param eters
used
in
the
simulation but there is no structural example of bent NO at the basal
plane
in
the
SP
geom etry.
However,
the
crystal
structure
of
RuH(NO)(Cyttp) shows highly distorted TBP, actually between SP and
TBP. Therefore, it is reasonable to assume the distortion of SP toward
TBP,
which have
equatorial
position
a few examples
such
as
in
of significantly
bent NO
in
the
R u I(N O )(C O )(P P h 3 )2 (1 5 9 (2 )°)
and
C o (N O )C l2 (P M eP h 2 )2 (1 6 4 °), has occurred in this case. Consequently, a
slightly bent NO group can be rationalized even though the degree of
bending is small. A bent NO group is expected to show restricted rotation
around M-N bond due to its double bond character for which canonical
structure 2 is the major contributor as aromatic nitroso compounds, (eq.
87
+ F = N/
M
M— N
(62)
Thermodynamic
b a rrie r
of
values
ArNO* 6 2
r e a r r a n g e m e n t s
and 23).
function
are
(process
com parable
12)
with
and
the
o th e r
163 including Berry pseudorotation
in tram o lecu lar
process (process
13
However, AS* of process 12 is too large for intramolecular
rotation and this indicates that a highly polar transition
solvation
rotational
entropies
are
im portant
m ight
be
i n v o l v e d .
state
164
T h c
where
o n iy
possibility is that the proton which might be present in trace amount in
the solvent (CD2 CI2 ) might catalyze the rotation process as follows (eq.
63 ).
/ °
N
~
*
-
. Z
5
-H+
M------
(63)
Limited
solubility
in common
organic
solvents prevents
of the solvent effect to check this possibility.
determination
Also, at 180K, peaks of
mer-RuH(NO)(ttp) start to broaden while the facial isomer peaks are still
88
sharp.
This might be due to lower solubility of mer-RuH(NO)(ttp) than
fac-RuH(NO)(ttp)
form only.
or
some
fluxional
process
involving
the
meridional
No conclusion was made since a lower temperature limiting
spectrum could not be obtained.
In the simulation o f
NMR spectra,
only two structures (I and II) were considered due to limitation of the
simulation
program
but good
agreement was obtained.
In order to
isolate the two isomers, refluxing in benzene for 30 min. (longer reflux
produces
the
ttp
oxide
and
other
uncharactcrized
products)
and
reduction of RuCl(NO)(ttp) with NaBH4 were done but no success was
obtained.
S tru c tu re s
Therefore, assignment of IR spectra (Table 2) is not reliable.
o f [RuH 2 ( N O ) ( P 3 ) ] [ B F 4 J and
R eactions
w ith
L
(L= N eutral Ligand)
Protonation o f a coordinatively unsaturated metal complex to produce a
cationic hydride complex is commonly
r e p o r t e d .
165
a classical example
of this reaction can be found in the Vaska complexes. 166
Recently,
molecular hydrogen complexes have attracted interest as a model o f H2
activation
which,
in
turn,
is
im portant in
the
hydrogenation
process
catalyzed by the metal complexes. Since the first discovery of this kind
of complex by
many
K u b a s l 6 7 ?
two
m olecular hydrogen
the hydride complexes
r e v i e w s 1 6 8 . 1 6 9
complexes
1 7 0 , 1 7 1 , 1 7 2 , 1 7 3
are
have been published.
prepared
and cationic
containing strong trans ligand (H, C O )169
by
d 6
Since
protonation
174
of
complexes
favor m olecular hydrogen
complexes, the possibility of molecular hydrogen complexes in the title
complexes was investigated.
Molecular hydrogen complexes are usually
characterized by NMR methods (T i
measurement and measurement of
89
JH-D).
***•
m ethod. 175
recovery
neutron
diffraction*****- 169 an(j
electroch em ical
redox
por [RuH2 (N O )(C yttp )]B F 4 , Tj measurement by the inversion
m ethod
and
attem pts
[R u (H D )(N O )(C yttp )]B F 4
to
m easure
the
Jh -D
in the
were made, but in the etp complex, attempts to
isolate and even confirm the existence o f title complex in situ by NMR
failed,
presumably
compound.
owing
to
the
extrem ely
unstable
nature
of
this
T i ,min of [RuH2 (N O )(C yttp )]B F 4 was recorded as 147 msec at
220 K.
This value is relatively high for a molecular hydrogen complex
(usually
T ivalues are less than 80 msec), but as Kubas pointed
this value is in the "gray area".
o u t ,
attempt to measure Jh-D
An
17(5
in
[R u (H D )(N O )(C yttp )]B F 4 failed due to fast exchange between two hydride
ligand s.
S e le c tiv e
decou p lin g
of
resonance
frequ en cies
of
the
phosphorus peak does not help to identify this value.
Hydride peaks
which
peaks
are
broad
at
temperature lowers.
however.
room
temperature,
becom e
the
Therefore, it is concluded that this complex has two classical
report
determined
c r i t e r i a *
as
Limiting, well resolved spectra cannot be obtained,
hydride ligands, not a molecular hydrogen ligand.
recent
two
that
by
a classical
NMR
method
hydride
shows
However, there is a
com plex([R eH 6 ( P P h 3 ) 3 ] + )* 7 7
nonclassical
behavior
by
other
75 an(j the exact nature o f this complex remains uncertain.
the variable
throughout
temperature
the
whole
experiment,
temperature
In
^ 1 p NMR spectra do not change
range
(190-303K )
but
*H
NMR
spectra show that the hydride at -5.37 ppm is trans to central phosphine
(2jp_H = 62 Hz) and the hydride at -8.95 ppm is trans to NO.
The hydridic
character is also confirmed by the IR spectrum where v r u _ h appears at
1950 and 1850 cm'*; NO seems to be linear and VNO appears at 1750 cm'*.
B J f * 4C C r T T P t t « r < P 31 t x X i K
!{
J
. k
I
-—
■ ■, _ . .
_
i
—
_
-
^
—
-
1
-J
v»
-A _
x _
JV
_/v_
A _
/X
A
X
' 1 1 " “I 1
4®
-*9
3*
_
A
■
2:
1-------------------------- —
2S
36
3*
P P tt
r
22
■
: ■ 20
t
■ ■
ia
21. V a r ia b le T e m p e r a t u r e S l p ^ H }
■— - ■ — —
‘. 6
!4
■
■
J2
■— 1— •— r ~
!0
0
N M R S p e c tr a o f
[ R u H 2( N O ) ( C y t t p ) ] B F 4 in CD 2 C I 2 a t 101.252 M H z
303K
9
353 msec
270K 266 msec
260K
237 msec
250K 00„
222 msec
240K
160 msec
230K
162 msec
220
171 msec
K
-\ 5 5
■)4 7 msec
200K
^
180 msec _
msec
/\ 163 msec
190K
A 174 msec
L_____________
7
- 3. 0
I......................
-3.5
-.0
-..5
- 5. 0
T
-5.5
- 6 . 0 pp- 6 .5
.
-7.0
Fig. 22. V ariable T em p e ra tu re
-7.5
-8.0
' -B.i"-s.'o"
NMR Spectra an d T i of
[ R u H 2 ( N O )( C y ttp ) ] B F 4 in CD 2 C12 a t 250.133 MHz
i
92
I
l#0
*
1000
600
measured as % transmission.
Fig. 23. IR S p ectru m o f [R uH 2 ( N O ) ( C y t t p ) ] B F 4 in C H 2 C I 2
93
There are two possible mechanisms to explain this exchange behavior
(eq. 64 and 65 ).
~]+
^ -P
f'-l
C <
" Hb
1 +
.
I N ta
<
“ J+
_ ^ H b ______ P . . . I - 'H a
f - J
1
^P
/ —P
H a^
OvT I >Hb
^P
^P
(6 4)
p.. I .'Hb
I JR u L
CN^ I
Ha
^ 7
_
-
E tl-
I
■H + H :C (^
CN< |
..H a
P -. I ,
I -R u ^
>Hb
CN
1
r
Et
(65)
However, for the HD complex, there is no change in the intensity of the
hydride peaks in the presence of a large excess of HBF4 -Et2 0 for a fairly
long time (~3 hr.)
m ech an ism ,
an
h y d ro g e n * 68,171
.which supports the previous mechanism.
e q u ilib riu m
b etw een
h y d rid e
and
In this
m o lecu lar
rotation about M-H2 bond 178,179,180 are assumed
and these phenomena have been reported recently.
Even though there
is no spectroscopic evidence except a very weak peak at 2650 cm '* in
the
IR spectrum
reactivity
toward
for the
presence
neutral
ligand
molecular hydrogen ligand.
of m olecular hydrogen
strongly
indicates
the
complexes,
presence
of
Generally, neutral ligands such as PMe3 ,
D 2 , CO, and CH3CN replace the H2 easily.
In these reactions, H2 bubbling
can be observed.
Also, application of vacuum induces loss of H2 followed
by
activation
the
solvent
by
the
reactive
16-electron,
4-coordinate
complex: when the reaction is run in CH2 CI2 , evaporation of the solvent
+
94
followed by addition of Et2 0 produces RuCl(NO)(Cyttp) in high yield and
reaction
in
ether
c h a r a c te r iz e d
without
H2
c o m p le x ,
cis-dihydride
hydrogen
easily,
an
incom pletely
[R u (N O )(C y ttp )]B F 4
or
Even though some hydride complexes
ligands
these
yields
p re s u m a b ly
[ R u ( N O ) ( C y ttp ) ( E t2 0 ) ] B F 4 .
containing
atm osphere
undergo
reactions
elim ination
of
req u ire
som e
usually
m olecular
external
assistance such as heating, irradiation or application of vacuum,*65 5^
to date, there is no example where Et2 0
can eliminate these hydrides.
However,
is
for
the
N2
reaction
which
one
the
of
characteristic
reactions of molecular hydrogen complexes, very complicated products
resulted but no title complexes were left.
reactions
This might be due to further
between coordinated N2 with HBF4 -Et2 0 present in excess in
the system or decomposition owing to instability of the N2 complex.
instability
The
of N2 complexes might be due to the positive charge and
presence o f NO ligand which causes the electron deficiency around the
metal.
Substitution of H2 by PMe3 shows that incoming PMC3 ligand just
occupies the position where molecular hydrogen left, the equatorial site
in the TBP; however, more bulky PPh3 cannot coordinate to the metal
center mainly due to steric hindrance imposed by the Cyttp rings, and
4-coordinate
(or
solvent
adduct)
complex
is
produced.
Meanwhile,
successive addition of HBF4 -Et2 0 and PMe3 to RuH(NO)(etp) produces the
P M e 3 adduct where PMe3 occupies the apical site trans to the central
phosphine.
This
product
was
crystallography ( see Fig. 24 ).
hydrogen, if present, occupies
equation
66 ).
the
stru ctu rally
determ ined
by
x-ray
This result indicates that molecular
apical
site
in
the
TBP
(
95
Rui
ND
(66)
In the [R u(PM e3)(N 0)(etp)]+ complex, NO is linear (175.1(6)°) and Ru-N
distance
(1.771 (5) A)
is
com parable
w ith
that
of
RuH (NO )(Cyttp)
(1.783(4)A) or RuH(NO)(PPh3)3 (1.792(11)A), but NO distance (1.160(6)A)
is considerably shorter than those values of RuH(NO)(Cyttp) (1.186(5)A)
and
RuH(NO)(PPh3)3 (1.183(11)A) which indicates less rc-back bonding
to the NO group as expected from the charge of this complex.
, selected bond lengths and bond angles are listed.
geometry, and overall geometry o f this complex
distances
arc
longer
expected
(vide
than
supra).
the
The
7
etp adopts facial
is TBP.
R u-chelating
phosphine
products
the
of
In Table
Ru-P-Me3
distance
reaction
as
between
RuH(NO)(etp) and H B F 4.E t20 vary with the solvent, which indicates that
1 6 -e le c tro n ,
4 -c o o rd in a te
[R u (N O )(etp )]B F 4 formed
molecular hydrogen might react with solvent.
with
loss
of
The products are listed
in Table 8. From this table, it is clear that in the absence o f rather
strong ligand such as CH3 CN or acetone, [RuH2 (N O )(e tp )]+ reacts with
ether
to
give
(presumably)
8Pw ing. 62.65 ppm;
ppm;
[Ru(ether)(NO)(etp)]+ (8P c e n te r; HO ppm;
2Jp .p , 9.6 Hz; 8(CH ?CH3). 4.75ppm; 8(CH2CK3J, 1.62
JH-H, 7.3 Hz).
However, in CH2 C I2 .
another
minor
product
(S P center. 107.47 ppm(br); 8P\ying» 75.17 ppm(br), Jpp, 24.3 Hz ) which
24. X -ray C rystal S tru c tu re
[ R u ( P M e 3)(N O )(e tp )]C l'C 6H 6
97
has a strange peak at 8.7ppm in the *H NMR spectrum is produced and
deuterium NMR confirms that its origin is from the metal hydride.
Exact
formulation of this complex cannot be made due to failure of isolation.
It is assumed that [Ru(NCCH3 )(N O )(etp )]B F 4 is produced in CH3 CN and
[ R u (a c e to n e )(N O )(e tp )]B F 4 in acetone but no further investigation to
fully
characterize
purification.
these
com plexes
was
made
due
to difficulty
in
When N2 is blown for 20 min in CH2C12. different products
from
the above complexes were obtained but,
peak
assignable
to
reaction between
were obtained
N2 stretching
frequency
in the IR spectrum,
can
be found.
In
no
the
[RuH2 (N O )(C y ttp )]B F 4 and CO, initially two products
but in nitromethane-d3 , only one product was detected.
At this point, no explanation for this can be made.
CS2
reacts with
[RuH 2(N O )(C yttp)]B F4 to give analytically pure [Ru(CS2)(N O )(C yttp)]B F4
but almost identical 31 p and 1H NMR spectra with the product of the
reaction between [RuH2 (N O )(C y ttp )]B F 4 and vinyl methyl ketone makes
this assignment suspicious.
Also, the reaction of RuH(NO)(Cyttp) with
H B F 4 in ether without an H2 atmosphere yields the same product from
the 3 1 p NMR spectrum.
as
Therefore, this product might be reformulated
[Ru(NO)(Cy tt p) ]B F4 ,
but
the
stability
of
this
complex
dichloromethane indicates that this is not a
16-electron species
16-electron species
are expected to be very
reactive as seen in
reaction
betw een
R uH (N O )(etp)
However,
vinyl
methyl
ketone
produce q 2 _0iefm complexes.
and
reacts
HBF4 in
with
d ifferent
in
since
the
solvents.
[RuH2 ( N O ) ( e t p ) ] B F 4 to
(31p NMR (acetone-dg); 31.48(d), 107.78(t),
2Jpp=13.1 Hz, *H NMR; 5(vinyl) 2.45, 1.45, IR(Nujol); VNO, 1600 cm '1* v c o ,
1700
cm'l
which is assigned on the basis of similarity of 3 1 p
spectra with q 2 -acetylene complexes ( Table 20 ).
NMR
98
T able 7. Selected Bond Distances and
Angles of
[ R u ( P M e 3 )(N O ) ( e tp )] C l
A to m s
D ista n c e s,A
A to m s
A n g le ,d e g
Ru-N
1.771(5)
N-Ru-Pi
127.0(2)
Ru-Pi
2 .3 3 3 (2 )
N-RU-P 3
12 3.2(2)
R 11-P 3
2 .3 3 5 (2 )
N-Ru-P 2
9 5 .8 (2 )
RU-P2
2 .3 4 1 (2 )
N-Ru-P 4
90 .6(2 )
RU-P4
2 .3 7 5 (2 )
P 1 -RU-P 3
10 8 .7 9 (6 )
N-O
1.160(6)
P 1 -R 11-P 2
8 1 .5 9 (6 )
P 1 -RU-P4
9 3 .7 7 (6 )
P 3 -RU-P 2
8 1 .3 5 (5 )
P 3 -RU-P4
9 6 .0 0 (5 )
P 2 -RU-P4
1 7 3 .5 3 (7 )
0
1 7 5.1(6)
-N-Ru
1. Standard deviation is shown in the parenthesis.
2. P i, P 2 , P 3 and P 4 represent wing, central and wing phosphines of
etp and PMe3, respectively.
Table
8.
31p
NM R
betw een
p a ra m e te r s fo r the p ro d u c ts o f reactions
R u H (N O )(etp)
and
H B F 4 in Different
S o lv e n ts.
Sovent
8 P center
8 P w in g
2 Ppp
CH3CN
96.65
5 9 .79
17.9
E th e r
109.97
6 2 .69
9.7
CH2CI2
110.72
62.65
9.6
107.47(b'
75.17(b )
24.3
101.24(b '
70.06(b )
21.7
100.34
73.5 4
18.2
101.24(b;
70.06(b )
21.7
A ceto n e
NMR
Solver tComment
C D 3C N
C D 2CI2
ft
ti
Acetone-d 6 initial
ft
tf
ft
after30min
1.Chemical shift is shown in ppm relative to 85% H 3 P O 4 . Positive
value represents downfield shift from external standard.
2
. b means broad
3. Coupling constants are given in Hz
Table 9. 3 l p NMR and IR Data for the Selected [Ru(L)(NO)P 3 ] B F 4
P3
C y ttp
L
P c e n te r
8
P w in g
PM e3
1.50
11.62
CH3O
17.45
2J
8P l
PP
S o lv en t
v(N O )
O th e rs
51.8,28.9,23.5
CE>2C12
1650
4.85
33.0
CE^CN
17 90
2 2 8 0 (w )l
-0.13
24.85
35.6
18 20
?
-6.06
17.37
30.8
28.03
19.64
23.6
5.02
22.31
40.9
-1.40
16.56
4 0 .4
n2
12.18
15.53
26.3
b z -d 6
CS2
13.96
16.54
26.3
c d 2ci 2
PM e3
97.34
71.85
185.5,33.4,20.9
A c e to n e
2 2 .8
A c e to n e
SO2
CD
e tp
8
101.54
n2
70.08
1. v(CN), w means weak
2. v (CO)
3. IR spectra are obtained in Nujol Mull.
-14.79
-4.57
tt
A c e to n e
ti
CE>2C12
1690
19502
1 5 90
18502
1760
16 70
!
~r
12
I
*7"
10
6
PPM
-0
n—
- 10
—
r—
-1 2
r~
-1 4
-1 6
101
Fig. 25. 3 1 p { l H } NMR Spectrum of [Ru(PMe3) ( N O ) ( C y t t p ) B F 4 in Acetone-d6 at 101.252 MHz.
Ju_
T 1100
90
80
T™r"
70
gp
■fVMM
■^T^
60
50
PPM
40
30
■^r
20
~-h10
102
Fig. 26. 3 lP { lH } NMR Spectrum of [Ru(PM e 3 ) ( N O ) ( e t p ) ] B F 4 in Acetone-d 6 at 101.252 MHz
103
C.
Structures
S ubtle
and
R eactions
change
complexes can
of
o f RuCI(NO )P 3
coordination
sphere
of
induce the change of NO
geometry of a transition metal
c o m p le x .2 5
5 -coordinate
bonding mode
nitrosyl
and overall
Therefore, it is interesting to
see what happens if the hydride is replaced with the chloride ligand in
the
RuH(NO)P3.
H o ffm a n n 2 5
argued that for the ML4(NO) where L is a
strong donor ligand, the final geometry would be SP with apical bent
NO, but pseudorotation from SP to TBP with equatorial linear NO would
compete with
it.
influence o f ligand
geometry is
However, the experimental evidence relevant to
donor properties on
not decisive.
Considering
the M -N -0
the
angle or overall
the trend that halide ligands
favor the process where overall geometry is SP with a strongly bent NO,
while hydride
h a lid e ),29,
favors the TBP with a linear NO in [IrX(NO)L3 ]+ (X=H or
42a, 127 jt
js
expected that RuC1(NO)P3 would prefer SP with a
bent NO group.
1.
Structures
o f M X(NO )L 3
Laing and Roper 1 81 reported that in the series of zerovalent ruthenium
com pounds,
RuX(CO)(NO)(PPh3)2 where X is halide, hydroxyl or various
other anionic ligands, the frequency v n Ovaries from 1642 c m 'l for X=I
to 1555 cm"* for X=OH, whereas VCO
series.
remains constant throughout the
This indicates a change in the bonding mode o f nitrosyl ligand
depending
on
the
nature
of
ligand
X.
C rystal
structure
of
R u I(N O )(C O )(P P h 3 )2 was determined by Hall^O but reliability of the data
is suspicious.
In this structure, Ru-N bond distance, N -0 bond length
and Ru-N-0 angle are reported as 1.80(4)A, 1.15(5)A and 159(2)° while
104
overall geometry is TBP.
On the other hand, more reliable structures of
[ I r X ( N O ) ( C O ) ( P P h 3 ) 2 ]+ (X=I,
Cl)29
were reported by Ibers.
These
complexes have SP geometry with apical bent NO group (Cl; 124(1)°,
1=125(3)° and PPh3*s are trans to each other.
toward the CO ligand.
NO eclipses the X-Ir-CO axis
Ir-N and Ir-C distances (1.97(1)A, 1.86(1)A) in the
chloro complex are longer than those (1.89(3)A, 1.70(5)A) in the iodo
complex
which
indicates
However,
in comparison
complex,
no significant
iodine is
with
a better n -donor
the N -0
elongation
of
bond
the
than
(1.16(1) A)
N -0
chlorine.
in
chloro
bond (1.17(4)A)
is
observed in the iodo analogue.
S p ectroscopic
Data
of
R u C l(N 0)P 3
Spectroscopic data of R uC1(NO)P3 are summarized in Table 9. The first
noticeable
feature is that there are two isomers in the Cyttp and ttp
complexes
and ratios o f two isomers are exactly reverse in the two cases.
One isomer (A) has a triplet far downficld from a doublet in the 31p NMR
spectrum while the other (B) has a 2nd order pattern.
On the basis of
the trans ligand effect on the 31 p NMR spectra discussed before, it is
expected that A has a weak trans effect ligand, Cl in this case, placed
trans to central phosphine whereas B does not have a trans ligand at all.
Refluxing the solution docs not convert one isomer to the other.
NO
stretching frequencies in the IR spectra (~1500 cm’ l for isomer A; ~1600
c m '* for isomer B) strongly indicate that isomer A has a bent NO group
while isomer B has a linear NO group, because almost the same NO
stretching
frequency
in
the
RuH(NO)P3 correspond to the linear NO.
From the spectroscopic data, it is concluded that isomer A has SP with
bent NO but isomer B has TBP with linear NO ( equation. 67 ).
P^
^C l
Iso m e r A
ls o m e r B
From a sim ilar NO stretching frequency, RuCl(NO)(etp) is assumed to
have the same type o f structure as isomer A.
was found in
R h C l( e tp ) .!
82
Meridional geometry of etp
Possibility of dimer indicated by the poor
solubility of RuCl(NO)(Cyttp) is contradicted by mass spectroscopic data
and can be discarded.
(718) is observed.
(No peaks over 1000 and a strong parent peak
Other peaks over 730 (m/e) may be the result of
recombination of dissociated ions.).
These types of isomers can also be
found in the series of CoCl2(NO)L2(L:
m o n o p h o s p h in e ) .4 4 ,4 5
pointed out that the magnitude of v ^ O
gross
stereochem ical
packing
and
lim iting
forms
change
proposed
of
a
difference (100 c m '* ) is due to
rather than
a change
conform ational
5-coordinate
Collman45
transition
merely
equilibrium
metal
in
crystal
betw een
nitrosyl
two
com plexes.
Considering another explanation
for the isomers in the above system,4
th e s e
shed
R u C 1(N O )P3
isom erization
31p
NMR
in
the
spectra
m ight
some
5-coordinate transition
of
R uC1(NO)P3
insight
in
the nature
m etal-nitrosyl
clearly
favor
of
complexes.
"hybridization"
equilibrium proposed by Collman because a difference of the bending
plane of the NO group should
much ,if any.
not
change the pattern of 31 p
spectra
The reason why a different isomer is more favorable in
Cyttp and ttp complex cannot be explained clearly, but it is evident that
T a b le 10. S p ectro sco p ic D a ta fo r R u C1(NO)P3
31P NMR
P3
Cyttp
ttp
e tp
8 P center,ppm
8 P wing,ppm
2Jpp, Hz
Solvent
23.03
37.08
19.49
15.32
37.6
CD2C12
33 .3 4
20.48
107.87
16.67
18.74
6 7.12
v(NO),cm-l
1495
43.7
IR
m e d iu m
Nujol Mull
15 90
46.6
40 .0
CDCb
20.1
CD2 CI2
15 10
16 10
14 80
T ab le 12. S p ectro sco p ic D a ta fo r R u C l 2 L 3 ( C O )
Geom etry
cis
L3
Cyttp
tr a n s
cis
Cyttp
ttp
ttp
tr a n s
cis
tr a n s
PM e 2 Ph
PM e2Ph
18.81
-18 .6
2 1 .2
-10.2
31P NMR
32
5.25
10.1
41
6.0
34
44
9.6
IR
Benzene
1935
Csl
re fe re n c e
this work
Toluene
143
CH2CI2
143
tt
143
1952
19 80
CHCI3
tt
191
191
* Chemical shift, coupling constants and NO streteching frequency are measured in units of ppm, Hz and
107
i - _L- 1
*9
3»
1
lr>
37
1
1*
L
L_J
36
T
33
35
1
32
34
T
31
—
1________________________________________
J
1
L
33
T 30
32
- r
29
31
f
20
30
--T 27
29
-1
26
26
•
“T
26
27
• • 7
24
26
PPM
't
p2 )
25
T "
22
24
“ '7
21
23
’T
20
22
21
T ---- “ T - “
19
|«
J
20
I"
|7
—
1
10
L
16
17
ft
------ » -------- ~ T --------------- J------- T
16
15
14
|j
Jl
fJt ------ ft1----- ft"
•
Fig. 2 7 .3 1 P {lH } N M R S p e c tra o f R u C l(N O )(C y ttp )(a ) a n d
R u C l(N O )(ttp )(b )
in
C D 2C12 a t 101.252 M H z
1
— ------ —
12
j|
108
1000
isoo
(b)
Fig. 28. IR Spectra of RuCl(NO)(Cyttp)(a) and RuCl(NO)(ttp)(b) in Nujol
* measured as
Mull
% transmission.
109
this
is
dependent
on
electronic
factors
rather
than
steric
factors
because bending plane of the NO group should involve P c e n te r-R u -C l
axis
if
steric
Hoffmann's
difference
in
em pirical
this
is right and there is no
e x p e c ta t io n ^
plane
for
either
complex.
No
observable
change of ratio of isomers under refluxing conditions indicates a high
activation barrier in the isomerization process.
X-ray
Crystal
Structure
of
RuCl(NO)(Cyttp)
The crystal structure of isomer A of RuCl(NO)(Cyttp) is SP about the
ruthenium atom with apical, bent NO group (Fig.
).
2 9
The ruthenium
atom is displaced from the basal plane toward the NO ligand
as in the case of [Rh(NO)Cl(ttp)][PF6]
the considerable deviation
Table
1 0
).
from
( 0 . 2 5 5 ( 4 ) A
the
ideal
)
t and this results in
) 2 3 a
angles
( 0 . 3 4 3 7 ( 9 ) A
among ligands(
see
The displacement of the title complex is greater than that of
isoelectronic rhodium complexes and this seems to be related to the size
of the central atom
because deviation of Ru(O) complex is comparable
with analogous Ir(I) com p lex .^a,
Also,
1 2 8
H o a r d ^ pointed out that
ionic radii of metal atoms are related to this type of deviation in the
phorphyrin system.
Ru-N distance
than that of the hydride analogue
[ R h C l( N O ) ( ttp ) ] [ P F 6 ]
( 1 . 8 4 7 ( 3 ) A
( 1 . 7 8 3 ( 4 )
longer
A) but shorter than that of
This
( 1 . 9 0 9 ( 1 5 ) A ) .
is significantly
)
is
as
expected
because
RuH(NO)(Cyttp) has a linear NO and jr-back bonding from metal center
to NO is greater than in RuCl(NO)(Cyttp).
has
a
positive
charge
and
ttp
unfavorable for 7t-back bonding.
M-N-O angle (RuCl(NO)(Cyttp),
N -0
bond
length
is
less
Meanwhile, [RhCl(NO)(ttp)]+
basic
than
Cyttp
which
is
These factors are also reflected on the
1 3 5 . 8 ( 3 ) ° ;
(R uC l(N O )(C yttp),
[RhCl(NO)(ttp)]+,
1 . 1 8 6 ( 5 ) A
;
1 3 1 . 0 ( 1 . 4 ) °
and
[R hC l(N O )(ttp)]+,
110
1.081(16)A). The Ru-N distance in RuCl(NO)(Cyttp) falls in the lower
limit of strongly
c o m p a ra b le
bent NO complexes reported to
to
th e
R u -N b en t
date.
d is ta n c e
This value is
( 1 .8 6 ( 2 ) A )
in
[R uC l(N O )2(P P h3)2][P F 6]3^b where the angle of RuNO is 136(1)°.
From
the reported literature,8,29,37b, 184 jt can be found that the angle of MN -0
becomes closer to 120° with the increase of M-N distances.
N -0 bond
length is not sensitive to the structural change and it is not surprising
that NO bond length in RuCl(NO)(Cyttp) is almost identical to that of
(1.18 6(5) A)
in
R uH (N O )(C yttp).
RuCl(NO)(Cyttp)
Ir(III)
H ow ever,
Ru-C l
is somewhat longer than those
com plexes.
R u C 1 (N 0 )(S 0 4 )
2.394A;
mer-
[R uC l(N O )2(PPh3)2][PF6]-C 6H 6,37b
( P P h 3 )2 ,1 8 6
[ I r C l( C O ) ( P P h 3 ) 2 ] [B F 4 ],2 9 b
in
o f Ru(II), Rh(III) or
( m e r - R u C l3 ( N O ) ( P P h 3 )2 , 2 3 C f
R u C l3 (N O )(P P h 2 M e)2 ,185 2.398A;
distan ce
2 .2 8 9 A ;
2.343A;
[R h C l(N O )(ttp )][P F 6 ] ;
R uH C l(PPh3 ) , 152 2 .4 2 1 A;
R u C l2 (P P h 3)3>1^7 2.388A) NO bends in the plane of Pcenter-Ru-Cl toward
P c e n te r
as expected.
whereas
this
structure
(RuH(NO)(Cyttp)).
structure
o f the complex, i.e. the presence of the other ligand on
same
ring.
plane
value
of
Bite angle of triphosphine is approximately
becomes
chelating
more
than
of
the
center
(93.61(2)°) in the TBP
Therefore, it appears to be related to
triphosphine
This compressing effect results
hydrogen
90°
phosphine
m ight
compress
in closer
phenyl
90°
the
and
the
chelating
contact between
ring
the
th at
of
the
the
cyclohexyl ring of the wing phosphines(2.31lA).
R ea c tio n s
As expected from
the long Ru-Cl bond distance, a
PM e3
the chloride ligand from the coordination
displaced
neutral ligand such as
sphere
to
29. X-ray Crystal Structure of RuCI(NO)(Cyttp)
( Isomer A )
112
T a b le
11. S elected
B ond
D istan c es a n d
A ngles o f
R u C l(N O )(C y ttp )
A to m
B ond
R u-N
D is ta n t e
A to m
Bond
1.847(3) A
N-RU-P 2
9 3 .7 (l) o
RU-P 2
2 .2 4 0 (1 )
N -R u-P i
9 7 .6 (1 )
R u- P i
2 .3 8 4 (1 )
N-RU-P 3
9 8 .2 (1 )
R 11-P 3
2 .3 9 3 (1 )
N -Ru-Cl
1 0 4 .3 (1 )
Ru-Cl
2 .4 7 7 (1 )
P 2 -R u -P i
9 0 .4 9 (4 )
N -O
1 .1 8 6 (5 )
P 2 -RU-P 3
8 9 .1 4 (4 )
P 2 -Ru-C1
1 6 2 .0 3 (4 )
P 1 -RU-P 3
1 6 4 .2 0 (4 )
P l-R u -C l
8 8 .3 9 (4 )
P 3 -RU-CI
8 7 .1 1 (4 )
0
1 3 5 .8 (3 )
* P i , P 2 an d P 3 re p re se n t w in g ,
re sp e c tiv e ly .
c e n te r
and
-N -Ru
w in g
p h o sp h in e s,
A ngle
113
yield
[Ru(PMe3 )(N0 )(Cyttp)]Cl which was confirmed by the 3 1 p NMR
spectrum.
However, the reaction did not ursh completion even with a
large excess of PMe3 and a long reaction time.
enough, lithium
alkyl
(phenyl
or methyl) compounds do not produce
Ru(alkyl)(NO)(Cyttp) as expected.
for
one
day
yields
only
Moreover, surprisingly
A reaction with a large excess of LiMe
unidentified purple compounds
insoluble in every common organic solvent.
which
are
The same reactions with
the aid of AgN0 3 or TINO3 produce a new complex (31p NMR (benzene):
8P Ce n te r 53.78 ppm, 8P w ing» 26.62 ppm, J p .p , 38.4 Hz) but the same
product is observed when [RuCl2 (Cyttp)] reacts with Tl(OEt).
purify
this
complex
prevents
further
investigation
for
Failure to
identification.
Also, it must be mentioned that a large excess of LiPh reacts with
RuCl(NO)(Cyttp)
to
produce
an
uncharacterized
complex
(3 I p
NMR
(benzene); 8P Center» 10.10 ppm, 8P wjn g, 19.10 ppm, J p p , 44.7 Hz) which
shows the 3 1 p NMR pattern as expected for Ru(Ph)(NO)(Cyttp) in the
NMR tube experiment but
produce the same result.
in the large scale experiment, it fails to
This result is not common but recently, the
same result was observed by
B ianchini.l^O b
j n hjs paper, [(NP3 )R h C l]
fails to react with alkyl lithium compounds, while [(PP3 )RhCl]
react. (NP3, N(CH2CH2PPh2)3; PP3, P(CH2CH2PPh2)3)reacts
slowly
with
[RuCl(NO)(Cyttp)]
CDCI3 to produce a new compound.
identify this complex, reactions with HC1 and HBF4 -Et2 0
and these produce the same
does
In order to
were performed
product as in CDCI3 (31p NMR (CD2 CI2 );
8P Center> 3.66 ppm, 8P w i n g, 9.25 ppm, Jpp=23.4 Hz).
Since no hydride
was detected in the *H NMR, this product was initially formulated as
[Ru(NHO)Cl(Cyttp)]X (X=C1 or BF4).
However, NO stretching frequency
(1840 cm‘ 1) is higher than those reported for N or O bound NRO (R=H or
114
M e)
c o m p le x e s
(O s(N H O )(C O )C l2 ( P P h 3 ) 2 , 3 9 *88
1410
c m '1;
[Co(das)2(NHO)Br] [C104]2,20 1560 c m 'l; Ru 3 ( C O ) i o ( N O C H 3 ) , 8 6 922 cm 'l,
R u 3 (C O )io (N O H ),S 6 m o
C m 'l, C p C o (R N O )(P P h 3 ) ,93 1480 -1300 c m 'l).
Several theoretical calculations* 8 8»*89**90 Would lead one to expect that
NO stretching of NHO would be at 1584 cm '*.
Since this value (1840 cm'
1) is usually observed in the ionic complex during this research, this IR
stretching should be assigned as the linear NO where no hydrogen is
attached to the N or O atom.
Elemental analysis strongly suggests that
this complex can be formulated as [RuCl(NO)(Cyttp)][BF4]2 which is the
product of oxidative addition of HX followed by loss of H2 -
Likewise, the
product of the reactions between RuCl(NO)(Cyttp) and CDCI3 , HC1 or
benzoyl chloride can be formulated as [RuCl2(NO)(Cyttp)]Cl.
Oxidative
addition reaction reported in the similar complex RuCl(NO)(CO)(PPh3)2
can
support
reaction
the
above
pathway (eq.
assumption. 1 8 1
68 ) is proposed.
Q
(68)
Therefore,
the
following
10
NMR
Spectrum
of [RuCl(N O )(Cyttp)][BF 4 ] 2 in Acetone-d 6 a t 101.252 MHz
115
Fig. 30. 3 lp { lH }
PPH
-2 0 0 0
(S0O
(OOD
cmH
* measured as % transmission.
Fig. 31. IR Spectrum o f [RuCl(NO)(Cyt*p)]fBF4] 2 in Nujol Mull
117
However, the reaction pathway through N-bonded (NRO) complex might
not be effective in the case o f reactions with CDCI3 or benzoyl chloride.
In the CDCI3 solution, RuCl(NO)(Cyttp) of SP geometry was detected with
the product [RuCl2(NO)(Cyttp)]Cl while RuCl(NO)(Cyttp) of TBP was used
up after 2 days.
[RuCl2(NO)(Cyttp)]Cl
does
not react with
dimethylsulfate any more but slowly reacts with HBr.
sim ilar,
but
with
pattern in the 3 1 p
phosphorus
NMR
bromide is a better n
resonances
spectrum
donor and
was
this
or
After 1 day, a
located
fu rth er
observed.
increases
acid
upfield,
Considering
the
electron
that
density
around the metal center, 31 p NMR data indicate that the bromide ion
substitutes for the chloride ion and produces [RuBrX(NO)(Cyttp)]X (X=Br
or Cl).
A reaction with CO initially yielded two complexes: (3 1 p
NMR
(benzene); complex A, 8P center> 17.99 ppm, 8P w ing. 4.46 ppm, Jp p = 3 1 .5
Hz;
complex B, 8P CCnter. 4.46 ppm, 8P w ing> 21.51 ppm, Jpp=41.2 Hz), but
after washing with acetone, complex A can be isolated.
Since cis- and
trans- RuCl2 (CO)(Cyttp) and RuCl2(CO)(ttp) show almost the same trend
(Table
12 ) in the 3 I p NMR spectra, and cis-RuCl2 (C O )(C yttp)
shows
almost identical 3 1 p NMR and IR spectra, complex A ( v n o = 1945 c m 'l,
V C0= 1955 c m 'l)
trans
to
each
js assigned as RuCl(NO)(CO)(Cyttp) where CO and NO are
other.and
complex
B
is
assigned
as
an
isom er
of
RuCl(NO)(CO)(Cyttp) where NO or CO is trans to central phosphine but
exact geometry cannot be deduced due to failure to isolate.
If isolated,
the 1 3 c NMR spectrum will show the exact geometry of this complex.
Reduction o f RuCl(NO)(Cyttp) with NaBH4 in ethanol for 2 hours usually
gives
a
m ixture
in
which
the
presence
of
RuH (N O )(C yttp)
R u H (B H 4 )(Cyttp) is confirmed by 3 1 p NMR spectrum.
minute
reaction
produced
mixture
containing
and
Meanwhile, a 30
RuH(NO)(Cyttp)
and
an
118
unknow n
green
com pound,
one
ch aracteristic
stretching of bridging BH4 (2400 (br) c m 'l).
tentatively formulated as Ru(BH4 )(NO)(Cyttp).
of
which
53,54,55
frequency
is over
1850 c m 'l
one 0f the intermediates
can
(excepting
IR
Therefore, this complex is
Since
RuH(NO)(Cyttp)
does not react with NaBH4 and usually nitrosyl complexes
stretching
was
react
with
whose NO
nucleophiles,
RuH(NO)(Cyttp))
should
have linear NO, the stretching frequency of which is around 1860 c m 'l.
The exact mechanism for producing RuH(BH4 )(Cyttp) is hard to propose
due to no available data about the intermediate but it should include the
step where BH4 anion attacks an NO group to possibly produce NH3 as a
side product.
A reaction between RuCl(NO)(Cyttp) and dimethyl sulfate
yields a mixture, and 1 h NMR spectra (complicated peaks at 0.5 - -2ppm)
indicate that addition of methyl cation occurs at the metal center but not
at coordinated NO group because N or O bound methyl group peak
appears downfield (~3 ppm).^3
119
D .R e a c tio n s
b etw e e n
H y d r id o n itr o sy l
R u th en iu m
C o m p le x es
and
Alkynes
1.
I n t r o d u c t io n .
The
reactions
between
alkynes
and
transition
metal
complexes
have
drawn attention due to their implication in the catalytic processes such
as hydrogenation, oligomerization and polymerization.
important
between
classes
alkynes
of
reactions
in
and transition
this
metal
field;
one
There
is
the
are two
interaction
and the other is the
insertion
reactions of alkynes to metal hydride or -alkyl bonds.
These reactions
and
places
catalytic
reactions
lite r a tu r e . 1 9 2 -1 9 8
type
of
products
are
well
reviewed
several
in the
jn thjs section, a brief review isclassified by
from
the
reaction
between
alkynes
and
transition
metal complexes.
2. On ^ - A c e t y l e n e
a)
S tructure
C o m p le x e s )
and
(a)
bonding.
(b)
(c)
(d)
Fig.32 M olecular Orbital Interactions between Acetylene
and Metal Ceter
the
120
The
nature
of
bonding o f side-on
coordination o f alkyne
has
been
discussed in detail by Jonassen et. al.1^2; this interaction is summarized
in Fig. 32.
The nature of bonding depends on the extent of overlap and
the
level
energy
difference
between
these
interacting
orbitals.
The
interaction shown in (d) o f Fig. 32 is not energetically significant due to
poor overlap
but the other interactions
the overall bond strength.
auxiliary
are important in determining
Since oxidation state of metal, the nature of
ligands and the substituents on the acetylene determine the
energy levels of metal and acetylene orbitals, these parameters should
be considered in understanding the nature o f bonding o f coordinated
acetylene.
In terms
of
the
additional
jc-donor
interaction
ambiguous
position
because
electron ligand.
proper
sensitive
it can
are
found
to
in
complexes (C-C
behave
either
transition metal complexes
symmetry
1 .3 5 A) 1 9 9 ,2 0 0
counting
rules,
available to acetylene places
is
available,
behaves as a four-electron donor.
are
electron
as
the
it in
a two
an
or four
In general, acetylene behaves as a two electron ligand
but in some early
with
sim ple
this
property.
it
is
where vacant d-orbital
apparent
In general,
donor
bond length;
acetylene
As expected, structural parameters
somewhat
carbon-carbon bond and shorter
4-electron
that
complexes
than
1.28A). 198 Longer
longer
(1.33-
metal-carbon distances
in
2-electron
donor
C-C bond length
and
bending o f C=C-C angle (usually 143 ± 5 ° ) are largely attributed to the
interaction (b).
In some c a s e s ^ ^ c ^ rotation of coordinated alkynes are
monitored by NMR spectroscopy but details on the mechanism are not
known to date.
b)
S p ectro sco p ic
D ata
121
1)
IR
S p ectro sco p y
Theoretically,
with
three
m etal-acetylene
fundamental
b o n d i n g ^ O l
IR
stretching
frequencies
associated
are expected if the system is regarded
as a vibrationally isolated, triatomic, isosceles (C2v
local symmetry)(eq.
69)
vi(a i)
v 2(a 2)
v 3 (b!)
(69)
However, V2 and V3 have never been assigned due to extensive coupling
with
other vibrations of the
decrease o f v j
frequencies
rest of the molecule.
The
degree of
upon coordination from the free acetylene IR stretching
depends
on
the
oxidation
donating ability of the auxiliary ligands.
state
of
metal
and
electron-
For example, IR stretching
frequencies of acetylene in Pt(II) complexes appear at about 2000 cm" 1
but in Pt(O) complexes, they are in the range of 1680-1850 cm 'lisostructural
iridium
com plexes,
jn
v i decreases with an increase in the
electron donating ability o f the auxiliary ligands.
Otsuka et. al. 2 0 2
tried to measure the metal-acetylene donation and/or back donation by
checking the NC stretching value in a series of complexes, M(Un)(tB u N C )2 (M=Ni, Pd,
Un=olefin
or
acetylene);
Pd
complex
represents
higher back donation to acetylene than the Ni complex and olefin and
acetylene show comparable re-accepting ability in the Ni complex.
122
2) 13 c
NMR
sp ectro sco p y .
Templeton et. al.^03 jjave suggested that there is a correlation between
the
electron-donor function o f an
acetylene
shifts of the acetylenic carbon atom.
they
found
the
following
ligand
and the chemical
From the survey of the literature,
three
regions ; however, chemical shifts of
1.4-elcctron donor: chemical shift of
spans 190-250
ppm.
2.3-eicctron donor: chemical shift o f
spans 130-170
ppm.
3.2-electron donor: chemical shift of
spans 100-120
ppm
acetylene
carbon
in
upfield as high as
2
4-coordinate
acetylenic
carbons
acetylene
complexes
goes
ppm. (trans-[PtM e(M eC =C M e)(PM e2Ph)2]+ P F 6 ‘
6 9 . 5
Also there are some
0 4 )
platinum
are
out
e x a m
of
p l e s 2 0 5
the
where
above
chem ical
range.
shifts
Therefore,
of
this
generalization needs some caution.
c)
The
R e a c tio n s
implication
of variable
electron
donation
is
also
shown
in the
reactivity
pattern.
In the ligand substitution reaction
to prepare the
acetylene
complex,
M (CO)(RC=CR)(dtc)2
^wo 2-electron
( M = M o , W
) , 2 0 6
donor ligands are replaced by a single acetylene molecule.
these
reactions
proceed
olefin is very slow.
very
To
fast,
date, olefin
w hile
substitution
Moreover,
reaction
with
analogs o f alkyne complexes are
known only for cases where acetylene is regarded as a 2-electron donor.
Term inal
alkynes
can
vacant drt orbitals are
isom erize
a v a ila b le .2 0 7
to
vinylidene
(eq.70 )
com plexes
where
no
H
123
C
II
I
M—
m
M
O— Cl
fR
R
M oreover, in
some cases,
n u cle o p h ilic
attack
fea sib le.208 (eq#
R
I
£'
M— HI
71
coordinated
in c lu d in g
acetylene
in tra m o le c u la r
is
(70)
so
activated
that
rearran g e m en t
is
)
R
I
Nu
:Nu
/
C
M— C
— —
fI
0" '
,R
"o rr
. _
\
^
N
Nu
R
/
r
(71)
M etallocyclization
with
other acetylene molecules
or small molecules
such as CO and RNC is frequently observed. ^ 8 (eq. 72 and 73 )
R
C
R
d'c c r '
R
R
/^ C R
M-HI S225— M
cI
cr
R
R
I , ------------------ ^
CR
^(R. C F C R )/ !
(7 2 )
124
o
CR
M
RCCR
M(CO)
VO
T
R
M-
r s cr R
o
(73)
3.
A lkenyl
These
C om plexes
title
m olecules
complexes
to
have been
m etal-hydrogen
nucleophiles to T ^-allen e
in te rn a l
a c e ty le n e .2 1 0
prepared
by
alkyl
bond
or
insertion
or
by
com plexes^!? or protonation
However,
only
insertion
of acetylene
addition
of
o f coordinated
reaction
will
be
discussed in relation to this research.
a)
G eom etry
1)
te rm in al
of
A lkenyl
acetylene
C om plexes
(R C = C H )
There are four possible product forms (eq.
the literature (Table
13
)
74
) and all can be found in
125
T a b le
13.
G e o m e try
T e rm in a l
R
o f A lk en y l
C o m p lex es
D e riv e d
fro m
A c e ty le n e s
C o m p le x
P ro d u c t
Type
re fe re n c e
Re(CO)5H
1
2 1 1 ,2 1 2
CpFe(CO)2 H
1
212
CP 2 M 0 H 2
3
213
CN
CpW(CO)3
1
214
CN
C p 2MH2(M=M o,W)
1
215
Ph
R3SnH
1
216
C4H 9
R3SnH
1
217
PtH 2(PR 3)2
4
218
CMe3
Cp*HfH2
2
219
C4H 9
Cp2ZrHQ
2
220
C M e3, Ph, Me
Cp*MH2(M=Zr, Hf)
2
221
CC>2Me
HMn(CO)s
1
222
Ph, n-C3H 5
RuHCl(CO)(PPh3)2
2
223
"
2
224
cf3
C02Me,CN,CF3
C02Me,C02Et,C0M ;
CC^Et
Co(N(CH2CH2PPh2)3)] I
3
225
CCbEt
Ni(N(CH2CH2PPh2)3)
1
225
Ph
RuH Cl(CO )(P-i-Pr3)2
2
226
Ph
O sHCl(CO)(P-i-Pr3)2
2
226
cn , cf3
Cp 2 MH(CO)(M=Nb,Ta )
3
241
R V -/H
.. / V
H
LnM
1
L"M
2
D
LnM
H
4
3
(74)
2)
Internal
acetylene
( R O C R 1)
Both cis and trans additions (eq. 75 ) are observed and the literature
survey is shown in Table 14.
R’
T ra n s ad d itio n
C is ad d itio n
(75)
b)
M e c h a n is m .
Several mechanisms have been proposed to explain the geometry of the
alkenyl
complexes,
but
solvent effect is scarce.
investigation
As
of the
H e rb e ric h l4 3
e t.
kinetic
a i.
has been difficult to predict the type of product
C o n ce r ted
(a)
concerted
m echan ism
cis
m e c h a n i s m 2 2 5 > 2 2 9
* 8 ,2 6 7
an(j
pointed out, up to now it
Also, easy isomerization
processes make the situation even worse in some cases.
(1)
d a ta 2
127
T ab le
14. G eo m etry
In te rn a l
R
CF3
Ph
R'
CF3
Ph
o f A lkenyl C om plexes
D erived
A c e ty le n e s
C o m p le x
G eom etry
HMn(CO)5
HRe(CO)5
Cp2MoH2
Cp2WH2, Cp2ReH
cis
IrHCl2(PM e2Ph )3
Pt HCl(PEt3)2
CpRuH(PPh3)2
tr a n s
Ref.
227
228
229
21 3
231
230
232
233
229
234
cis
23 5
236
233
23 7
229
RhH(CO)(PPh3)3
Cp2MoH2
IrH(DMSO)Cl2
PtHCl(PEt3)2
CoH(DMG)2
C 0 2Me
C 0 2Me
from
RhH(CO)(PPh3)3
CpCoH(PPh3)
Cp2MH2( M=Mo,W)
tr a n s
MnH(CO)4(PPh3>
Cp2ReH
222
238
232
CpRuH(PPh 3 )2
239
2 2 2 ,2 4 0
cis
233
RhH(CO)(PPh3)3
Ir(H 2)(a-carb)(CO )(RC N )(P P h3) tr ms 242
RhH(CO)(PPh3)3
MnH(CO)5
Ph
C02Et
C 0 2Me
C 0 2Me
it
242
224
RuHCl(CO)(PPh3)3
CC^Et
C 0 2Me
CN
COMe
C 0 2Me
CN
Cp2WH2, Cp2ReH
Cp2ReH
cis
243
243
128
This mechanism was proposed to explain stereospecific cis addition of
hydride to alkenyl moiety.
(76)
(b)
con c e rte d
This mechanism
trans
m echanism ^ 1 3
formally belongs to a thermally
reaction utilizing the acetylene n ±
orbital.
allowed
A nonpolar four-centered
hetcroatomic tranisiton state with a skewed disposition
a - and n- bonds may be postulated.
(77)
(c)
stepw ise
ionic
m echanism
225,244
[a 2 s + 7t2s]
of participating
(d)
ra d ic a l
This
m echanism
mechanism
rad ic al
2 1 7 ,2 4 5
produces
p a ir
the mixture
m echanism
req u ires
of cis
and
trans
isomer
ste ro sp e c ific p ro d u ct
but
(trans
iso m er).218
A cetylide
a)
C om plex
S tru c tu re
an d
b o n d in g
To date, reported acetylide complexes show that this metal-carbon bond
is
more
stable than
the
corresponding
metal-alkyl
metal-carbon bond was attributed to du-pn back
but
from
shortening
the
available
which
o b se rv e d .2 4 7 ,2 4 8
is
the
jn a
crystal
structure,
bond.
bonding
significant
consequence o f rc-backbonding
A
strong
i n t e r a c t i o n ^ 6
M-C
is
bond
scarcely
recent report249, Bartczak et.al. compared the 7t-
acceptor ability of acetylide ligand with that of CO in the closely related
complexes.
They found that n interaction in the acetylide complex is
negligible or none due to a longer M-C bond
( 2 .0
complexes (1.869(2)A).
pointed out that there is
However,
N a s t 2 5 0
16(3)A) than that of
CO
no
130
doubt about the n -acceptor properties of acetylide ligand in the anionic
"zerovalent"
transition
markedly low vc=C-
m etal.
b)
The
property
was
reflected
by
the
Acetylide ligand is essentially linear but in trans-
P t( C 2 P h ) C l( P P h E t2 ) 2 » ^ ^
( 1 6 2 ( 3 ) ° )
This
significant bending
of the M-C=C
angle
was found.
S p ectro sco p ic
characteristic
D ata
IR
stretching
band
for
acetylide
generally falls between
1950 and 2200 cm"*.
strong
is
but
sometimes
very
w e a k . 2
2
5
( v c = C)
ligand
This band is normally
This stretching band is
dependent on the nature of the alkyl group attached to the C=C
and the electron density on the metal atom 250 (^-back
unfortunately,
changes
in the frequency
and
in the
bonding)
intensity
directly relate to the electron density distribution in the O C
There are several
l i t e r a t u r e 2 5 3 , 2 5 4 , 2 5 5 , 2 5 6 , 2 5 7
reports
group
but
do not
g r o u p . 2 5 3
containing
NMR data of acetylide complexes. However, the trend and range of 8 C a
and 8C p are not consistent. 8 C a
appears as high as
usually falls in the range of 90-120 ppm as does 8C p.
acetylide
Ca
c o m p l e x e s ,
253
2 3 2
p p m 2 5
7 >
but
In the case of tin
this range shifts slightly upfield (75-120ppm).
appears downfield relative to Cp but the reverse trend is reported in
some other literature.
Therefore,
without the coupling constant data
between * 3 c and other atoms o f 1=1/2, it is difficult to assign Ca and Cp.
c)
From
R e a c tio n s
the
e x p e rim e n ta l 5 8 an(j theoretical
s t u d i e s , 2 5 9
the p carbon in
the transition metal acetylide complexes is electron rich and behaves as
131
a nucleophile toward reagents such as H+ ,260 M e + 2 6 0 b E t + ,261
halide
an(j
2 6 2
ligands.
The resulting complexes contain vinylidene
h a l i d e . 2 6 3
Recently,
organoboration
265
gj^yj
cycloaddition
reaction
with
activated
o l e f i n , 2
6 4
an(j vinylvinylidene synthesis with alkynes 266 are
re p o rte d .
R esults
In
this
and
Discussion
section,
reactivities
of RuH(NO)P3 and
[RuH2 ( N O ) P 3 ] B F 4
(P 3 =Cyttp, etp) toward acetylenes (internal and terminal; nonactivated
and activated acetylenes) were investigated.
Generally, RuH(NO)(Cyttp)
produces
acetylenes)
acetylide
(nonactivatcd
term inal
while RuH(NO)(etp)
reaction
rate o f RuH(NO)(Cyttp) is faster than that of RuH(NO)(etp)
ow ing
to
a
differences, (vide infra).
acetylene
reactions
acetylene reactions.
are
com bination
insertion
of
products
insertion
products
probably
produces
and
electro n ic
only.
and
The
structural
As expected, the reaction rates of the activated
much
faster
than
those
of
nonactivated
[RuH2 (N O )P 3]B F 4 gives ^ -a c e ty le n e complexes no
matter what type of acetylenes are used and the trend of the reaction
rate
rem a in s;ac tiv ated
nonactivatcd
and
internal
term inal
acety len es
analogues..
In
reac ts
the
fa s te r
m onohydride
reactions, hydride transfers to the terminal carbon
than
complex
atoms o f terminal
acetylenes and trans addition occurs when internal acetylenes are used.
a)
R eactions
between
R uH (N O )(C yttp)
nonactivated acetylenes ( R O C H ;
and
R=Ph,
term inal
(CH 2 ) s C H 3 )
- T -
31
~r~
30
~I—
29
I—
26
- r27
I—
26
I
- 124
25
—I23
—I22
—I21
—t20
—I—
18
T IB
PPM
132
Fig. 33. 3 1 P { lH } NMR Spectrum of R u(C C Ph)(N O )(C yttp) in C 6D 6 at 101.252 MHz
133
2.5
T r
8.0
“rT r"
7.0
T-
T
A*
6 0
Fig. 34. 1H NMR S p ectra of R u(C C P h)(N O )(C yttp) (a) before
and (b) a fte r tre a tm e n t o f acetone in C6D6
at
250.133
M Hz
134
CMJ ( H r
^
—
t
Fig. 35. ^ C ^ H }
-1131
“ T“
130
717
V
1?S
_
I? 6
D E P T NM R S p e c tra o f R u (C C P h )(N O )(C y ttp ) in
C D 2 C I 2 a t 62.896 M H z
135
* measured as % transmission.
Fig. 36.IR Spectrum o f Ru(CCPh)(NO)(Cyttp) in Nujol Mull
136
(1) PhC=C H
From the
NMR spectra taken after evaporating all solvents without
isolation, there are vinyl products which do not seem to be coordinated
based on the following experimental data.
(a) *H {31 p} NMR spectrum does not change the shape of the vinyl
peaks:
(3 sets of doublets, 1 doublet might be obscured by the phenyl
peaks); ranges from 5.5 to 6.1.
(b) In the
alkyne peaks
q
NMR spectrum, alkcne peaks (108.6,
107.7 ppm)
and
(141.6, 139.1 ppm ) are all singlets.
(c) After isolation of products, 3 1 p { lH ), 1 3 c and
NMR spectra do not
change except that the vinyl peaks arc gone.
(d) With excess phenylacetylenc, longer reaction times (2 days) made
these peaks grow.
Also, there is no geminal coupling (16.2, 11.9 Hz), and chemical shift
difference excludes the possibility
o f styrene.
(Chemical shift o f the
vinyl group of styrene in CDCI3 ; 5.24(dd), 5.74(dd), 6.72(dd) at
M H z ) . 268
Considering the result of Dobson et.
a l . , 2 6 9
9 0
an(j the fact that
chemical shift of vinyl peaks in ^H NMR go downfield, these vinyl peaks
can
be
assigned
to
cis-
R u ((P h )C H = C -C sC P h )
r e c e n t l y 2 7 0
and
X(Cyttp)
trans-l,4-diphcnyl-l-butene-4-yne.
Also,
(X=CC2 Ph, Cl) prepared in our group
jn which vinyl peaks appear at 6.1~6.3 ppm support the
above assumption. Moreover, an empirical formula of chemical shifts of
substituted
ethylene
given
by
S ilverstein^? 1 predicts 6.15,
6 . 9 8
ppm
(trans isomer) and 5.68, 6.73 ppm (cis isomer) which is close to the
experimental value (5.5,
6 . 0
ppm (cis); 6.1 ppm (trans)) except for one
137
value. In the IR
spectrum, there is no peak assignable to this organic
product. However, there is a medium peak at 1590 cm ' 1.(shoulder of v n O
at 1600 cm-1) Moreover, v c = C is weak when a triple bond is conjugated
with a double bond and value of v c = C
d e c re a s e s .2 7 2
Therefore, v c = C ° f
organic compounds might be covered by the strong peak of v c = C
organometallic compound.
No other peaks except reactant and product
assignable to the intermediate in the 3 1 p
the reaction are found.
NMR spectrum
taken during
For the organometallic compound, v c = C
NMR data (C-H correlation and DEPT experiment) strongly
acetylide
complex.(Table
a°d
support the
15 ) Based on these experimental data, the
following mechanism is proposed: (eq.79 ) In the first step, coordination
o f acetylene followed by internal rearrangement accompanying H2 lo ss
may compete with the oxidative addition process.
be rationalized by
(vide
undergo
infra).
oxidative
Moreover,
this process for acetylcne.281,282
for
further
process can
considering the fact that acetylene is a weak acid and
RuH(NO)(Cyttp) can
reagents
The latter
addition
of
acetylene
addition
there are
reaction
many
with
known
various
examples
of
Also, acidity of acetylene is important
to
produce
an
organic
compound.
When only one equivalent of acetylene is added, the reaction proceeds
very slowly.
possibly
This means that the coordination of acetylene is not easy,
owing
to
steric
concentration of proton.
hindrance - o f
Cyttp
ring
or
insufficient
No further investigation of solvent effect and
kinetic measurement was performed to verify the above mechanism.
PhCi
RuH(NO)(Cyttp)
Ru— C = C P h
Oxid. add.
PhCCH
PhCCH
C2Ph
fast
PhCCH
fast
*(NO)(Cyttp) moiety is removed for clarity
( 7 9 )
The structure of the acetylide complex might be TBP with equatorial NO
group because NO and CsCPh are all strong trans effect ligands. If either
of them locates trans to the central phosphine, chemical shift of the
central phosphine should go upfield significantly (vide supra).
In the
SP structure, either NO or C=CPh should be located trans to the central
phosphine.
spectra.
Also, the meridional form of Cyttp is confirmed by
Since VNO d ° es not
change
perceptibly
from
NMR
the
reactant
(RuH(NO)(Cyttp)) which has a linear NO group, NO seems to be linear in
this
compound
reactions
and
between
the
following
hydride complex
acetylides have been
r e p o r t e d . 2 7 3 , 1 2 3
structure
and
is
phenyl
proposed.
acetylene
Sim ilar
to
produce
I
T a b le 15. S p ectro sco p ic D ata fo r R u ( C 2 R ) ( N O ) ( c y ttp )
31p NMR
S o lv e n t"
R
2Jpc
v(NO)
v(CQ
13 l( d t) 18.6,2.3 124(t)
3.0
1605
2050
35.2
1 32(dt) 14.1,2.0
2.0
1605
1940
2 5.94
3 4 .4
133(t)
1600
1990
20.67
26.13
.3 5 .4
21.54
27.25
35.5
1605
2060
SP center
8 P wine
2Jpp
21.85
27.57
3 5 .2
(CH2)5CH 3
23.15
2 8 .5 2
COMe
20.38
CO2Et
CH2 OH3
Ph
Bz-d 6
IR2
13C NMR 1
SQx
2Jpc
SC*
120(0
9.5
1 18(dt) 21.0,7.2 1 19(s)
* This solvent is used for 31P NMR only.
1. For 13C NMR, CD2 CI2 is used as a solvent all the time.
2. IR spectra are taken in Nujol Mull.
3. In proton NMR spectrum,
5 (C H 2 )
is found as a broadsinglet
at 4.67ppm.
In IR spctra, OH stretching band is found as a broad band centered at 3300cm*1.
139
140
PCy2
P h Pp ------------------------F
u "
"
ND
PCy 2
(80)
(2 )
1 -o c ty n e
This reaction proceeds more
owing to steric
acetylide.
effect,
slowly than the
but produces the
above
same type of complex,
an
After comparing the spectroscopic data, the same structure of
phenylacetylide complex is proposed for the product.
produces
reaction, possibly
organic
c o u p lin g
(2.2
compounds
Hz)
containing
ob serv ed
olefin
in d ic a te s
C H 3 (C H 2 )5 C (C H 2 )C 2 (C H 2 )5 C H 3 .
th a t
Also, this reaction
m oiety.
th is
Geminal
m ight
be
Applying the empirical formula to
predict the chemical shift
of olefin hydrogens results in the shifts of
5.57 and 5.12 ppm which
is closely matched to the experimental data
(5.40, 5.10 ppm). A Different type of organic compound suggests that in
the
stage
of
production
of vinylidene
rearrangem ent
com plexes
in
mechanism
above,
2 6 0 b tQ ■q2.acejy]ene
nucleophilic
attack208a 0f acetylide would occur (eq. 81 ).
H
r1 +
the
proposed
followed
by
1+
C— C = C R
R
(81)
R
I
T
13
12
IH
PPH
Fig. 37. 31p{lH } NMR Spectrum of Ru(C(CH 2) C 0 2E t)(N 0 )(C y ttp ) in C6D 6 a t 101.252 MHz
I
-1
1
I
a .O
1
1
1
■
1
7.5
1
1
1
1
1
7 .0
1
1
1
1
6 .5
1
1
1
«
1
6 .0
1
1
1
'
I
5 .5
1
1
1
»
I
5 .0
»
'
, "1 ' I
»
■
1
4 .5
1
I
4 .0
i
■ •*
»' I
3 .5
1
1
1
1
I
3 .0
i t
-t - t ' T
2 .5
1 ' 1
1
1
I
2 .0
1
1
1
1
I
1 .5
1
1
1
1
1
1.0
1
1
1
» "'!
1
■
'
.5
Fig. 38. 1H NMR Spectrum of R u(C(CH 2)C 0 2 E t)(N O )(C y ttp ) in C6D 6 a t 250.133MHz
142
PPM
I
'
'
j
1
I
8-0
'
i
'
'
I T
7 .5
'
1 1
I ' 1
7 .0
1
''
1
I
6 .5
'
1
1
■
I
6 .0
r i
i
1
I
1
5 .5
»
■ T
5 .0
I
I
I
I
I
I
I
4 .5
<
II
I
,
4 .0
,
I
I
I
3 .5
I
■
I
I
I
I 1 - 1
3 .0
'
r ~i
I
■
I
I
S .5 3 .0
I
I
I
I
|
1 .5
i
i
,
I
,
,
10
, i
I
i
i
,
5
PPM
Fig. 39. !H NMR Spectrum of the
P ro d u ct of the
R eaction betw een R uD (N O )(C yttp) and
C H C C 0 2E t in C6D 6 a t 250.133 MHz
0 4
144
CH3 l» L T
A
.I
cm wi.r
A
- U
'.ZZ'"o»C^CZC£ET
lie
:6 e
!l
140
£:»
L
.
I'i C C IC .e
12&
ICC
5:
ec
«
20
PPH
Fig. 40. 13C{1H} D EPT NMR S pectra of
R u (C (C H 2 ) C 0 2 E t)(N O )(C yttp) in CD 2 C12 a t 62.896 MHz
1500
1000
so
145
* measured as % transmission.
Fig. 41. IR S p ectru m o f R u(C (C H 2) C 0 2E t)(N 0 )(C y ttp ) in N ujol M ull
146
The attack site of coordinated acetylene is determined by the stability of
the
208a
p r o d u c t .
jn thjs case, attack on the carbon atom bearing alkyl
group is favorable because less crowded Ca can be produced.
b)
R ea c tio n s
betw een R u H (N O )(C yttp)
and
term in al
activated
acetylene.
(1)
This
E thyl
Prop iolate
reaction
reaches
com pletion
coupling in the * H NMR and
alm ost
instantaneously.
Geminal
NMR spectra ( D E P T ) clearly show that
the product is an alkenylcomplex where C«
bears an alkyl substituent.
1 3 c NMR spectrum shows that Ca is located cis to both phosphines.
C = 1 4 .0 , 7 .4
Hz).
that NO is not
( 2 jp .
Also, 2nd order pattern of 3 1 p NMR spectrum indicates
trans tocentral phosphine.
IR stretching frequency of
NO does not change significantly but v c O
than that of free acetylene (1720 cm‘ 1)-
shifts to a frequency lower
This indicates some interaction
between oxygen of C O and the ruthenium metal atom.
However, strong
interaction
(i.e.
oxygen)
accompany
the change o f 3 1 p
coordination
through
NMR
7t-donation
spectrum
of
(triplet
should
should
move
downfield from doublet due to poor trans effect of oxygen). A similar IR
frequency was interpreted to be due to noncoordinated carbonyl group
in the related complex ( R u H C l( C O ) ( P P h 3 ) 3 ) .2 2 4
structure
is
reasonable for this product but
Therefore, the following
there
might
exist
weak
interaction between ruthenium metal and oxygen atoms because second
order pattern of 31pN M R spectrum
in te r a c tio n .
cannot
be justified
w ithout
this
147
ND
Ph
CH;
(82)
The nature of NO is not clear but the presence of interaction between CO
and
ruthenium
stretching
bending
indicates
frequency
of NO
some extent
does
group. (
v
n
not
0
of
reflect
= 1580
any
c m 'l .)
bending
even
indication
though
of
NO
significant
In order to determine the
addition mechanism, the same reaction was run with RuD(NO)(Cyttp).
The result shows that there is no preferential site between cis and trans
position.
The deuterium scrambled result indicates that ionic or radical
mechanism
works
in
this
system.
However,
cis
concerted
followed by isomerization cannot completely be excluded.
addition
This reaction
was run in the nonpolar solvent benzene, and this condition favors a
radical mechanism over an ionic mechanism.
Radical inhibitor such as
2,4,6-trimethylphenol does not make the reaction slower and attempts to
confirm
the
presence
spectroscopy failed.
o f radical
by ESR
(Electron
Spin
Resonance)
The stabilities of possible vinyl radicals (eq.83)
contradict the experimental
results.
The more
stable B form 274
complex as a product.
in
this
system,
product should
might favor Cp
alkyl
bearing
alkenyl
Therefore, concerted mechanism appears to work
but the
isom erization
be considered
process
after
forming
in explaining the deuterium
the
cis
scrambling
experimental results. There are several reports of fast isomerization via
or phosphine catalytic
r a d i c a l 2 7 5
r e a c t i o n . 2 7 6
However, in the present
system no possible external radical source can be found.
This leads to
the proposal of the thermal excitation process mentioned by Nakamura
et.
for r]2-acetylene
a l . 2 7 7
8+
g_
R u ---D
reaction.
R u-
E t0 2C —
8-
8+
( 8 4 )
If
the
product
is
stored
for
a
long
time
in
dichlorom ethane,
isomerization process is induced which probably involves
an
1,2-hydrogen
149
CO oEt
C O oEt
I
H
Ru-
/ '
•C
\
H
(85)
Isomer B has a similar chemical shift to isomer A (Table 16 ) and similar
A8(A8=8PCen tcr -8Pw ing) value to acetylide complex, but shifts upfield in
the 3 1 p NMR spectrum.probably owing to lack of II-back
bonding
of
acetylide group. Cis position of two vinyl hydrogens are confirmed by
NMR spectrum.
(No trans, cis coupling was seen but broad band
(( o i / 2 =>2H z) was observed ).
No further attempt to isolate this isomer was
made, and no IR data were obtained but due to the similarity of pattern
in the 3 1 p NMR spectra with acetylide complexes, TBP structure with
linear NO is assigned to this complex.
ND
Ph
Ru.
( 86)
T reatm ent
with
chloroform
alkenyl group is intact.
be
found
dim ethyl
in the
acetylene
produces
another
com plex
where
the
The only example of this type of reaction can
reaction
between
dicarboxylate
in
trans-[PtH(CH3 C N ) ( P P h 3 ) 2 ] + a n d
c h l o r o f o r m - d . 2 7 8
t0 produce cis-
[Pt(C(C02M e)CH C02M e)Cl(PPH 3)2]. The 13C NMR spectrum shows that the
150
alkenyl group is located trans to the central phosphine but cis to the
wing phosphines (2jp_c= 78.9, 10.6 Hz), and VNO shows typical cationic
complex frequency (1840 c m 'l). The 3 I p NMR also indicates that strong
trans ligand lies trans to central phosphine; a triplet appears upfield to
doublet.
In the
NMR spectra, no hydride is found.
Reactions with a
large excess of HC1 and HBF4 -Et2 0 in benzene produces RuCl(NO)(Cyttp)
and
an
unknown
compound,
respectively.
However,
amount of the same compound can be seen.
a
very
small
Therefore, electrophilic
attack by proton on N or O atom cannot be completely excluded but v n 0
(1840
cm"* ) is much higher than the reported value ( ~ 1600
) 210,275,276,277
cm" 1
Slight excess of HC1 in dichloromethane produces the
same product in CDCI3. Therefore, this complex might be formulated as
[R uC l(C (C H 2)C 0 2 Et)(N0 )(Cyttp)]Cl. The reaction pathway for this complex
appears
to
accompanied
involve
oxidative
by
loss
RuH(NO)(Cyttp)
the
can
of
undergo
addition
a
of
hydrogen
several
2
equivalents
m olecule.
oxidative
of
However,
additions
easily,
HC1
since
the
following alternative reaction cannot be excluded.( eq. 87 ):
R u (C (C H 2)C 0 2 Et)(N 0 )(C yttp) + CHCl3->
[ R u ( C H C l 2 ) ( C ( C H 2 ) C 0 2 Et)(NO)(Cyttp)]Cl
(87)
This type of reaction is reported only by Marder et. al. 278 for the
activation of CH2 CI2 by a rhodium complex.
However, in the ^H and
NMR spectra, peaks of CHCI2 cannot be found.
Based on the reported
data of 8(CHC1CH3) (5.17-5.32) in CpRh(CHClCH3)(P-iPr3)X (X=C1 or 1)90
and 8(CH2C1) (3.37-3.64) in [(dmpe)2 M Cl(CH 2Cl)]Cl-CH2 Cl2 (M=Rh, Ir) and
8(CH_Cl3) shifts downfield from 8 (CH_2C l2) by 2 ppm, 8 (CH_Cl2 ) might
appear around 5.0-7.0 ppm and 8 ( C H C l2 ) appears around 50-80 ppm.
1
10
1------------- '
8
1-----------1
6
1----------- '
4
1--------- '
2
1------- '
0
1-------------'
-2
1-------------1
-4
1------■
-B
1--------------■
-8
1-----------'
-10
1---------- '
-12
1---------- '
-14
1----------- 1
-16
-IB
1---------- '
1-----------1
-20
1-------- 1
-22
1—
-24
PPM
Fig. 42. 3lp{lH } NMR Spectrum of [RuCl(C(CH 2 )C 0 2 Et)(N 0 )(C yttP )]C l in CDCI 3
at
101.252
MHz
►
—
*
L/l
INTEGRAL
8.0
7 .5
7 .0
6 .5
6.0
5 .5
5 .0
4 .5
4 .0
3 .5
3 .0
2 .5
2.0
PPH
Fig. 43. 1H NMR of [Ru(C(CH 2) C 0 2E t)(N O )(C yttp)C l]C l in CDC13 at 250.133 MHz
n>
-
5 .8
-
6.0
_
6 .2
_
6 . 4
-
6.6
-
6.8
-
7 .0
-
7 .2
-
7 . 4
-
7 .6
-
7 .8
8.0
I
134
133
132
131
130
129
128
127
126
125
Fig. 44. C-H C o rre la tio n D iagram o f [R u(C (C H 2 ) C 0 2 E t)C l(N 0 )(C y ttp )]C l in CD CI 3
153
PPM
154
flUrt C K3 C*L?f
3JH
Ch
2 OM*
CH CNL i
160
:oo
: -iO
IOC
20
60
es
60
40
20
Fig. 45. 13C{1H} DEPT NMR S p e c tra o f
[R u (C (C H 2 ) C 0 2 E t)C l(N O )(C yttp)]C ! in CD CI 3
at
62.896
MHz
155
Therefore, there is a possibility that these peaks are close to those of
chloroform
However,
and these
no
extra
are obscured by the
peaks
were
observed
complexes, after the reaction with
solvent peaks
even
when
in CDCI3 .
the
isolated
CHC13, were dissolved in CD2C I2 .
Therefore, this formulation for this complex is not acceptable. When a
large excess of ethyl propiolate and a longer reaction time is used, a new
complex (31p NMR; 26.13(d), 20.67(t) ^3p.p= 35.4 Hz) is observed.
From
the pattern of the 3 1 p NMR spectra, it is assigned an acetylide structure
which might be formed with the loss of vinyl compounds.
(2)
3 -B u ty n -2 -o n e
These reaction products are dependent on the amount of acetylene and
solvent.
When
amounts
of two
1 equivalent amount of 3-butyn-2-one is used, equal
com plexes
are
produced.
High
isomer B from the NMR experiment; however,
tem perature
favors
refluxing the benzene
solution to isolate this complex produced some unknown decomposed
compound.
Based on the experimental data (Table 16 and 17 )
s im ila rity
of
s p e c tro s c o p ic
d a ta
w ith
fu lly
and
c h a ra c te riz e d
[R u (C (C H 2 )C C 0 2 Et)(N0 )(Cyttp)], these two compounds are assigned to
isomers of Ru(alkcnyl)(NO)(Cyttp)
which are sim ilar to those o f the
ethylpropiolate
above.
complex
discussed
The
reason
why
amounts of isomer B are produced in the present and in
propiolate
mechanism
with
reaction
competes
chloroform
exclusively.
is
not
with
converts
clear;
possibly
concerted
both
in
mechanism.
isom ers
At this point, the mechanism
to
this
different
the ethyl
reaction,
However,
one
treatm ent
com plex
which induces
radical
alm ost
these two
isomers to convert to [Ru(C(CH2 )COMe)Cl(NO)(Cyttp)]Cl is not clear. The
similarity of spectroscopic data to the data for the corresponding ethyl
I
Table 16 31P NM R
P3
C yttp
P a ra m e te rs
Alkenyl
8P center,PP m
8P wing,p p m
2J PP
S o lv en t
1 3 .1 2
1 4 .5 7
47.0H z
b e n z e n e -d 6
6.21
1 2.63
4 0 .4
ft
1 3 .2 2
1 4 .9 2
4 3 .9
ft
CHCHC02Et3
7.10
1 3 .2 8
4 0 .7
ft
C(C02MeX:HC02Me
9.55
1 2.9 3
4 5 .5
ft
C(CH2)Ph
9 3 .7 8
7 2 .9 5
15.1
it
C(CH2)C0Me
95.9 1
7 2 .2 0
15.3
CD2C12
C(CH2)C02Et
9 6 .4 9
7 1 .4 6
14.3
b e n z e n e -d 6
C(CH2)C0Me,A
'
CHCHC0Me3
C(CH2)C02Et,A
e tp
of R u(A lkenyl)(N 0)P 3
rs
C(C02MeX:HC02Me
9 5 .7 5
7 2 .8 2
1 6 .4
CD2 CI2
156
!
Table 17. *H NMR
P3
P a ram e te rs
A lk e n y l
fo r R u(alkenyl)(N O )P 3
8H v i n y l
2J p h
2J h h
C(CH2)COMe(A)
6.55(br,m )
CHCHCOMe(B)
7.85(m )
C(CH2)C02Et(A)
6.70(br,m )
CHCHCC^EtfB)
6 .5 0 (b r)
2.0
2.0
6.02(br,m )
2.0
2.0
5.06(br,d)
CCOfeXX®
4 .5 0 (b r)
O th e rs S o l v e n t
4.5
2.5
6.10(br,m )
11.3
1
B enzene
2
4.4
2.5
3
CD2C12
4
5 .8 0 (b r)
C(CH2)COMe
QCCbM eKHCO^ e
2J h h
6.8 5 (b r)
CCCChMeKHCO^ e
e tp
2J p h
cis (p)
tra n s (a )
Cyttp
8H v i n y l
6.51(br,d)
5.7
5
2.90(d)
5.6
6
2 .5 0 (b r)
3.69(s)
7
♦Chemical shift and coupling constant are shown in units of ppm and Hz.
1.8(Me); 2.45(s)
2. 8(Me); 2.66(s)
4.8(OCH2);4.13(q), S(Me); obscured
3.8(OCH2); 4.02(q), 8(Me);1.27(t), 3J h h = 7 .1
5.8(Me);3.80(s), 3.72(s)
6.8(M e);2.05(s)
7.8(M e);3.66(s),3.26(s)
-j
i
Table 18. 13C NMR and IR S pectra D ata for R u(alkenyl)(N O )P 3
A lkenyl
P3
5Ca
Cyttp C(CH2)C02Et(A)
164.8(dt)
2J dc
6Ce
14.0,7.4 125.5(dt)
4Jpc
7.4,3.7
SCO
Others v(NO) v(CO) v(C=Q
184.0(s) 58.891 1580
1 6 8 0 1585
14.842
(B)
128.0(br)
C(C02Me)CHC02 Me 192.7(dt) 12.7,8.1 126.8(d)
3.3
182.9(s) 51.42
1605
162.8(s) 51.22
e tp
C(CH2)COMe
169.0(td)
47.4,9.0 115.5(t)
7.4
211.4(s) 27.92
1675 1 5 2 0
1730
1620
1 6 5 0 1585
1570
C C O W Q zB
C(C02Me)CHC02h fe
122.7(t)
8.0
180.7(s) 50.72
162.7(s) 50.22
1620
1700 1580
1640
1730 1580
1700
* w e NMR and IR spectra are taken in CD2 CI2 and Nujol Mull, respectively.
* Chemical shifts, coupling constants and stretching frequencies are measured in units of ppm, Hz and
c n r 1, respectively.
1. 8(OCH2)
2. 8(Me)
00
T a b le
19.
S p e c tro sc o p ic
A lk enyl
159
o f [R u (A Ik e n y I)(N O )C I(C y ttp )]C I
31P NMR
8 P ceter
C(CH2)COMe -1 7 .8 6
C(CH2)C02Et -1 6 .8 1
QCOjMcXniCOjMc
D a ta
-1 2 .7 3
1H NMR
8P w ine
2J p p
§H vinyl
2J p h
4.75
2 6 .0
7 .0 (d )
15.8
6 .7 (d )
5.7
6 .7 5 (d )
14.9
6 .1 7 (d )
5.9
2 5 .4
4 .7 0
2 5.8
6.2 9
6.55
IR
13C NMR
5Ca
2J p c
5CB
2J p c
5CO
2J p c
v(NO)
1 6 8 .6 (td ) 79.6, 10.C 135.3(s)
2 0 4 .9 (s)
1830
1 5 2 .6 (td ) 82.0, 10.1 130.5 (s)
174.4 (s)
1840
1 6 7 .4 (td ) 78.9, 10.C 124.7 (s)
175.8(s)
1840
1 6 3 .5 (d )
9 .2
* Chemical shift, coupling constant and NO stretching frequency are
shown in units of ppm, Hz and cm-1.
* td; triplet of doublet, d; doublet, s; singlet
!
—r -
16
~r~
17
16
~r~
15
1
14
I
13
------- T”
12
11
!
n -----------r~
6
5
10
PPM
Fig. 46. 31p{lH} NMR Spectra of R u(C(CH 2 )C O M e)(N O )(C yttp)
R u(C H C H C O M e)(N O )(C yttp)
160
in C 6 D 6 a t 101.252 MHz
and
I
—r —\— i— | — i— i— i— i— ' | — i — i — i
B.O
7 .5
i
|
7 .0
i
i
i
i— |
6 .5
i
i
i
i ■|
6 .0
i
T -i-n — f i
5 .5
i
i
i
j
5 .0
i
i
i i— |
r
t — i —i— j— r
4 .5
4 .0
t
*
i
|
■»
i
i
3 .5
i— |
■»
3 .0
i i— i
J
2 .5
»
'
»
«
\
2 .0
•
— r— «— 1— 1—7 — 1— 1 1
1 .5
1 .0
1
|
1
1
1
.5
PPM
Fig. 47. 1H NM R S p ectra o f R u(C (C H 2 )C O M e)(N O )(C y ttp ) a n d
in
161
C 6 D 6 a t 250.133 MHz
R u (C H C H C O M e)(N O )(C y ttp )
i
6
t
5
— i----1
------------1
--------1
—— i---------------1
------1
----------1
---------1
---------1
----------1
---------1
---------1----------1----------1
----------1---------1
----------1
----------1
---------1
----------1
----------1
----------1
---------r---------1
—
4
3
2
1
0
-1
-2
-3
-4
-5
-6
-7
PPM
-8
-S
-1 0
-1 1
-1 2
-1 3
-1 4
-1 5
-1 6
-1 7
-IB
-1 9
-2 0
Fig. 48. 31p{lH } NM R S p ectru m o f [R uC l(C (C H 2 )C O M e)(N O )(C y ttp )]C l in C D C I 3
101.252
MHz
162
at
' I 1 «* 1I '
7 .5
7 .0
1" I ■ '
6 .5
1 1I 1 1 ' ' I 1
6.0
5 .5
T‘1 1
5 .0
T 1 1 111
4 .0
PPH
'■m
' 1 1 ■ T » « ■Tn_r
3 .0
2 .5
2.0
T
T
TT _r
1. 0
Fig. 49. 1H NMR Spectrum of [RuCI(C(CH 2 )C O M e)(N O )(C yttp)]C l in CDCI 3
at
250.133
MHz
T
5
jjii
210
200
190
180
170
160
150
140
■JJ
V.
130
120
110
PPM
100
90
80
70
60
50
40
30
L -k L
20
10
0
(a)
Fig. 50. (a) Normal ^ C p H } NMR Spectrum of [RuCl(C(CH 2 )COM e)(NO )(Cyttp)]Cl in CDCI 3
164
a t 62.896 MHz
165
1_*AA_AAa^
RUHNOCYTTP*CHCCOne ( 1 EG I
IN C0C1.3
I ____ A
135
13 5
134
1 33
132
131
PPV
13 0
1 29
- r *------------1---------------- >---------------- r
1 20
127
126
(b )
Fig. 50. (b) 13C { 1H} DEPT NMR Spectra(Phenyl region only)
o f [RuCl(C(CH2)COM e)(NO)(Cyttp)]Cl in CDC13 at 62.896
MHz
27
~~r~
26
“ in25
_
~T“
r
24
23
PPM
—r~
22
21
”1“
20
166
Fig.51. 3 lp { lH } NMR Spectrum of Ru(CCCO M e)(N O )(Cyttp) in C6D 6 a t 101.252 MHz
167
Fig. 52. 1H NMR Spectrum of R u(C CCO M e)(N O )(Cyttp) in CD 2 C12 at 250.133 MHz
168
propiolate complex is the basis for the above formula, and the fact that
peaks corresponding to CHC12 cannot be found in the *H and 13 C NMR
spectra supports this assignment over the coordinated CHCI2 complex
in case of ethyl propiolate complex discussed above.
as
A large excess of
acetylene induces formation ofan acetylide complex as seen before.
(3)
Propargyl
A lcohol
This reaction produces an acetylide complex which is rather surprising
because "OH is more acidic than sCH.
M a rd e r.^ l
The same reaction was reported by
In that reaction, the CH bond of CH=CR
(R=(CH2 )2 C 0 2 H ,
(CH 2 )2 0 H) is activated by [Rh(PMe3)4 Cl] rather than the O-H bond.
interesting
is
the
fact that this
acetylide
complex
produce a complex containing aldehyde group.
can
More
rearrange
to
13 C and *H NMR spectra
show characteristic features for this complex; (CD2 CI2 ) 170.1(S), 5 (£ H O );
9.40(t), 5(CHO), 3 JHH=2.6 H z ; 8(C H 2 ): 7.7(m), 31p NMR (benzcne-d6 ),
24.97(d), 19.33(t), 2 Jp .p = 3 4 .6 Hz.
This reaction is catalyzed by another
molecule of propagyl alcohol and without it, rearrangement reaction is
slow.
of
When 2 equivalent of propargyl alcohol was used, about 3:2 ratio
acetylide/aldehyde
alcohol
gave
was
produced,
acetylide exclusively
retention in the solution.
but
1 equivalent
but slowly
of
isomerized
propargyl
for a long
On the basis of experimental results, the
following scheme ( eq. 88 ) is proposed for this rearrangement.
The
first
and
equilibrium
appears
to
be
the
rate
determ ining
one,
protonation by another molecule shifts the equilibrium to the right.
169
+
Ru
Ru— C S C — CHgCH
R u = C — CH2-CHO
(88)
U nfortunately,
carbyne
difficulty
relatively
and
peaks
dilute
cannot be
detected
concentration
due
of
*3 C
to purification
NMR
sample;
therefore, it was not determined whether this reaction is catalyzed by
external
proton
source.
(4)
P ro p a rg y l
This
reaction
C h lo rid e
produces
RuCl(NO)(Cyttp)
which
was
discussed
before.
This result is also unexpected because all reactions of terminal activated
acetylenes
discussed
in this
section involve
the terminal C-H
bond.
However, there are several reports about the oxidative addition reaction
of RCeCX
(X=halide) where
C-X bond activation occurs, but
to my
knowledge, there is no precedent report on the preferred activation of a
C-X bond over a =C-H bond by the metal hydride complexes.
Meanwhile,
it is well known that benzyl or allyl halide can easily undergo oxidative
addition to d^
5-coordinate
c o m p l e x . 2 8 6
Since these reactions proceed
by a two-step reaction, stability of benzyl or allyl cation or radical
formed during the reaction may be important.
propargyl
cation
or
radical
can
acetylenic cation or radical is very
be stabilized
u n s t a b l e . 2 7 4
By the same token,
by
resonance
(eq 89 )
while
i
30
'
r
29
i
r
28
27
i----------------- 1------------------- 1-------------- 1------------------- 1----26
25
84
23
22
1--------------1-------------------- 1---------------- 1----------------r ---------
21
20
19
IB
17
PPH
170
Fig. 53. 31p{lH } NMR Spectrum of R u(C C C H 2 O H )(N O )(C yttp) in CD 2 C12 at 101.252 MHz
I
7 .5
7 .0
6 .5
6 .0
5 .5
5 .0
4 .5
Fig. 54. *H NMR Spectrum of R u(C C C H 2
4 .0
3 .5
3 .0
2 .5
2 .0
1 .5
1 .0
Q .Q
PPM
0
H)(N 0 )(C yttp) in CD 2 C I 2 at 250.133 MHz
171
8 .0
1VH931NI
7 .5
Fig. 55.
7 .0
6 .5
6 .0
5 .5
5 .0
PPM
4 .5
4 .0
NMR Spectrum of M ixture of R u(C C C H 2
3 .5
0
3 .0
2.0
H )(N Q )(C yttp)
0.0
and
R u (C C H 2 CH O )(N O )(Cyttp) in CD 2 C12 a t 250.133 MHz
N)
173
C H =C
C H 2CI = ^ C H z = C
C H ^ C r^ = ^ S H = C = C H ^ ]c r
C H = C — C H o + C I ^ ^ C H — C = C H 2 + Cl
R uH (N O )(C yttp) + CH— C CH 2C I
~ ~ \+
cr
-ch3c c h
R uC
X h fe C C H
n*
u
R u C I(N O )(C y ttp )
/
n +
c ! 7 6 h2CCH2
RuT
n ch= o
= ch2
(89)
Therefore,
oxidative
addition
of
propargyl
chloride
follow ed
by
reductive elimination of 1-propyne or allene is proposed as shown in
eq.
89,
Since this
reaction
radical process is favored.
was run in non-polar solvent, benzene,
This reaction proceeded quantitatively when
one
equivalent amount of acetylene was used, but a complicated mixture
was
obtained with a large excess of acetylene.
This result might be due
to further reaction of RuCl(NO)(Cyttp) with other radicals.
(c)
R eac tio n s
acetylene
This
betw een R u H (N O )(C y ttp ) an d
in te r n a l
a c tiv a te d
(M eC0 2 C = C C 0 2 M e)
reaction
proceed
very
quickly
to
result
in
the
trans
product. The geometry of the alkenyl group was confirmed
(In sen sitiv e
N uclei
Enhancem ent
by
P o larization
experiment.
This experiment shows that the
insertion
by INEPT
T ransfer)
resonance
NMR
of the
174
carbonyl carbon not bearing vinyl proton is split by 16.2 Hz. This value
indicates these groups to be trans to each
this reaction might be a radical one.
o t h e r . ^ 4 3
T h e
mechanism for
C lark ^l^ dearly shows that trans
insertion is the consequence o f a radical pair mechanism.
addition
followed
by
isom erization
geometry cannot be excluded.
radical is shown, (eq.
R
u - / -
S » fc
90
to
However, cis
therm odynamically
stable
Z
Proposed isomerization process involving
)
th6rmal
excitation
R u ^ rC
H
C w °
R u=C ^
>
OMe
CO^Me
'C M e '
‘cO gM e
C Q ,M e
COoMe
I
Ru— C
C 0 2Me
(90)
Also, the chemical shift of Ca (192.7 ppm) in the
NMR indicates one
carbonyl group coordinates to the metal center because coordination of
carbonyl
should
c h a r a c t e r . 2 8 4 (
as
in
the
e q
case
shift
91
the
peak
of
CO
dow nfield
due
to carbene
) Treatment with CDCI3 produces a similar product
of ethyl
propiolate and
3-butyn-2-one
and
in
this
complex, the chemical shift of C« moves upfield (167.4 ppm) due to lack
o f this carbene
p re s e n te d .
character.
This
indicates
that no coordinated
CO is
175
/° ^ C O M e
/^ C O M e
Ru
C
C
O2
Me
O2
Me
(91)
(d)
R eactio n s
betw een
nonactivated
A
reaction
owing
to
using
stcric
reaction with
R u H (N O )(C y ttp )
an d
in te rn a l
acetylene.
diphenylacetylene
interaction
proceeded
between
the
very
phenyl
slowly
ring
probably
and
Cyttp.
A
l,4-diphcnyl-l-3-butadiyne also proceeds very slowly. No
further attempts to isolate the products in either reaction was made.
(e)
P re p a ra tio n
of
V inylidene
C om plex
Protonation of acetylide can lead to a vinylidene complex^GOa orT^2.
a c e ty le n e . 2 6 0 b
Protonation
produces
complex.
vinylidene
of
The
phenylacetylide
carbene
com plex
character
product can be easily confirmed by the * 3 C and 1H
of
readily
C a in the
NMR
spectra.
8(Ca )(334.2 ppm (dt), 2Jpc=19.9, 12.6 Hz) and 5HvinyIidene (5.84 (td), 4JP .
H=12.4, 6.2 Hz) fall in the range of reported vinylidene complexes.
spectroscopic data are listed as follows. (31P
Other
NMR(Acetone-d6); SPcenter*
20.64 ppm, 8Pwing, 19.14 ppm, 2Jpp, 28.5 Hz, 13C NMR(Acetone-d6); SCp,
119.6(dt), 3Jpc,14.7, 6.7 Hz, IR(Nujol Mull); v(NO), 1670 c m ^ . v ^ C ) , 1640,
1615 cm-1) The nature of NO is not clear but the cationic complex is less
favorable for n-back bonding than comparable neutral complex.
shifts to higher frequencies.
vn
O
Therefore, it is concluded that NO might
15
—r~
14
—r*
13
12
PPM
“1
11
I
10
Fig. 56. 3lp{lH } NMR Spectrum of Ru(C(C 0 2 M e )C H C 0
101.252 M Hz
M e)(N 0 )(C yttp) in CD 2 C I 2
176
at
2
I
T* T ~1
6 .5
5 .5
5 .0
4 .5
4 .0
3 .5
3 .0
2 .5
2. 0
1 .5
T I—r
T
I '
,5
* 1 * I
0.0
177
Fig. 57. 1H NMR Spectrum of R u (C (C 0 2 M e ) C H C 0 2 M e)(N 0)(C yttp) in CD 2 C l2 a t 250.133 MHz
178
L£E CH3 <WLY
L E E CH
2 ONLY
- 1 1 ______
L E E CH ONLY
___
i
+.Jm
LffiCl3 C l3 33 ***-250-2
160
140
too
40
Fig. 58. 13C{lH} DEPT NMR Spectrum of
R u (C (C 0 2M e )C H C 0 2M e)(N 0)(C yttp) in CD2CI2
a t 62.896 M Hz
6 .4
6.6
7 .6
1
PPM
137
136
135
T
134
133
132
131
PPM
130
129
128
127
T
126
125
1 79
59. C-H C orrelation D iagram of R u (C (C 0 2 M e )C H C 0 2 M e )(N 0 )(C y ttp )
180
i
1 82 . 7
|-------------------1-------------------1-------------------,------------------ -—
102.6
102.5
102. 4
182 . 3
PPM
Fig. 60. 13C IN E PT Spectrum of
R u (C (C 02M e)C H C 02M e)(N 0)(C yttp) in CD 2 CI 2
( C arbonyl Region Only)
10 2 .2
181
be linear, and again TBP structure is assigned to this product. This
complex
undergoes
rearrangem ents
which
lead
to
closely
related
4
iso m ers.
PhP'
Ru:
ND
(9 2 )
On the
basis
acetylene
and
of Struchkov's
s tu d y ^ O b
making dim er through
rc-bond
molecule), and since 3 1 p NMR pattern
the
reaction
butadiyne,
between
these
might
(vinylidene converts to tj2 .
of acetylide of another
is close to that of the product of
[RuH2 ( N O ) ( C y ttp ) ] B F 4 and
be
r\^ -a c e ty le n e
1,4
com plexes
diphenyl-1,3-
or
flu o rin ated
compcxes. However, lack of data prevents further conclusions.
(f)
R eaction s
of
P h e n y la c e ty lid e
com p lex
w ith
other
acetylenes
In
order
to
confirm
w hether
exchange
of
experiments using phenyl acetylide complex
as
1-octyne
and
ethyl
propiolate
were
of
acetylene
another acetylide
followed
complex
by
occurs,
NMR
and other acetylenes such
run.
acetylide exchange reaction does not occur.
addition
acetylide
reductive
The
results
show
that
In other words, oxidative
elim ination
to
produce
appears unfeasible, (eq. 93 )
However, slow
formation of new complexes was confirmed by 31p NMR.
The pattern of
3 1 P NMR in the new complexes does not match with any of the well
j
I
I
I
PPM
of [R u(C C (H )P h)(N O )(C yttp)]B F4 in CD2C I2 a t 101.252 MHz
18 2
Fig. 61. 31p{lH } NMR S pectrum
JL.
6 .5
6.0
5 .5
5 .0
4 .5
4 .0
PPM
3 .5
3 .0
2 .5
2. 0
OO
Fig. 62. 1H NMR S pectrum
of [R u(C C (H )P h)(N O )(C yttp)]B F 4 in CD 2 C12 a t 250.133MHz
i
330
r~
337
I
336
I
335
I
I
334
333
PPM
I
331
~r~ —r~ ~1
330
3 29
328
I
327
(a)
1
124
I
123
1—
122
I
121
!
120
I
119
1—
118
PPM
I
116
(b)
Fig.63. 13c {1H} NM R S pectrum of [R u(C C (H )P h)(N O )(C yttp)]B F4 in CD2C12 a t 62.896 MHz
( (a) Coe , (b) C|3 )
185
established patterns of acetylide and alkenyl complexes.
Therefore, on
the basis o f known chemistry of acetylide complexes, the product might
be a coupling complex, (eq. 93 )
prevents
However, lack of a clean reaction
further investigation of these reactions.
H C=CR'
M— C
CR’
(9 3 )
(g)
R eactio n s
betw een
R u H (N O )(etp )
an d
acety len es
These reactions are slower than those of the Cyttp analogue.
The reason
is not clear, but accompanying structural changes during the reaction
might be the reason.
However, electronic factors cannot be excluded.
From the spectroscopic data discussed later, the NO group changes its
position from equatorial to apical in the TBP structure (eq. 94
).
This structure is not ideal because in the TBP, the jr-acceptor
ligand
favorably enters an equatorial position, but there arc some cases where
it is trans to a strong a
structure
as
in
donor and occupies
an apical
site
in TBP
RuH(NO)(PPh3 ) 3 , which seems to work in this case.
Reactions between RuH(NO)(ctp) and terminal
complexes
where
confirm ed
by
Ca bears the alkyl group.
DEPT
(D istortionless
acetylenes give
alkenyl
This type of product was
E nhancem ent
Transfer) experiment in case o f 3-butyne-2-one.
by
P olarization
In another acetylene
case, the similarity of the 31 p NMR spectra is the basis o f structural
assignments of the products.
isom ers
are
produced
at
In the reaction using ethylpropiolate, two
room
tem perature,
condition, only one compound is formed.
w hile
at
the
reflux
This phenomenon is exactly
opposite of that of the analogous reaction o f the Cyttp complex (3butyn-2-one produces 2 isomers but ethyl propiolate gives one product).
The reason is not clear yet.
Information about the insertion mechanism
187
is limited
(no reaction
m e a s u re m e n t
w as
of the analogous deuterium
not
dim ethylacetylcnedicarboxylate
ta k e n ) ,
but
reaction,
trans
by the INEPT experiment mentioned earlier
complex;
in
th e
addition
kinetics
c a se
of
was
confirmed
(^JC -H = 14.6 Hz).
One more
interesting feature is that the chemical shift of the vinyl group is far
upfield in the etp complexes compared to that in the Cyttp complexes.
No reasonable explanation is deduced yet. In the l^ C
NMR spectra, ^ Jp -C
of Ca (47.4, 3.0 Hz) indicates thatthe alkenyl group
is cis to the central
phosphine; 47.4 Hz is rather large in view of the corresponding value of
the Cyttp analogue (14.0, 7.4 Hz) but considerably smaller for the case of
[R u(A lkenyl)(N O )C l(C yttp)]C l
clearly
shows
that
the
(~80 Hz).
term inal
=CH2
Also, the DEPT experiment
group is present.
For the
backbone carbons, the carbon near the central phosphine and one near
the wing phosphincs can be easily distinguished by the value o f the
coupling
constant
between
carbon
and
central
phosphine
but
the
geometry cannot be deduced as in the Cyttp complexes due to lack of
data.
In the IR spectra, v n o
*s almost the same as the parent hydride
complex which indicates linear NO throughout these types of complexes.
(h)
R eactio n s
betw een
G enerally,
these
substitution
o f dihydrides
pathways
neutral
can
ligands
[R uH 2 ( N O ) ( C y t t p ) ] B F 4
reactions
be
(or
expected
are
produce
ti 2 - ace ty le n e
m olecular
from
accompanied
acetylene reactions, characteristic spectroscopic
were obtained
(Table
20
and 21
These
that
H2 bubbling.
A cetylenes
com plexes
hydrogen).
the observation
by
and
reaction
reaction
For the
via
with
terminal
data for i\2 - a c e t y l e n e
). However,
nonactivated
internal
W wM ww* w%Mvvr«v
T
100
98
T
96
94
9*2
90^
bb"
T
~I—
84
PPM
0^
Ho
~r
78
72
70
"ee
66
188
Fig. 64. 31P{lH} NMR Spectrum of [Ru(C(CH 2 )C O M e)(N O )(etp)] in CD 2 C I 2 a t 101.252 MHz
JU
1I 111 ' I ' ' ' 1I
7 .5
7 .0
6 .5
1 i i i I i
6.0
t '1
5 .5
'■ 1 1 I '
5 .0
' I * 1' i '
4 .0
PPM
3 .5
T "1
3 .0
i—p-i
2 .5
r-|—'
2.0
T
T
1 89
Fig. 65. 1H NMR Spectrum of [Ru(C(CH 2 )CO M e)(N O )(etp)] in CD 2 C12 at 250.133 MHz
T
190
•4^*
11
j |
Fig. 66. !3C{1H} DEPT NMR S pectra of
[R u (C (C H 2)COM e)(NO)(etp>] in CD2C12 at 62.896 MHz
191
181
180
PPM
Fig. 67. 13C IN EPT NMR Spectrum of
[R u (C (C H 2)C O M e)(N O )(etp)] in CD2C12 a t 62.896 MHz
192
acetylenes produce complexes that have not been fully
No clear pattern in the 31 p NMR
co m p le x e s
w as
characterized.
like that found in the monohydride
o b se rv e d .
T he
s tru c tu re
of
[ R u ( ti ^ -
ace ty le n e)(N O )(C y ttp )]B F 4 is assigned as TBP with linear NO because in
the cationic complex, it-back bonding which induces NO to bend is not
favorable.
Since r\^-acetylene occupies the position on the equatorial
plane in the TBP^, the following structures
are appropriate to these
complexes (eq. 95 ). In the proposed structure, two isomers are possible
for an unsymmetrical acetylene, i.e. positions of R and R' are reversed.
In
the
phenylacctylene
occupy the
case,
the
carbon
bearing
hydrogen
tends
to
position trans to center phosphine on the basis of the
proton NMR spectrum where
is 22.8 Hz; however,
NMR spectra
does not follow this conclusion since 2 jp _ £ 's are only 14.5 Hz.
PhP.
PhP'
CR’
CR
CNl
A
(9 5 )
The 13C NMR results indicate that structure A contributes more to the
actual configuration than structure B even though this does not explain
why the proton feels
structure B more than does the carbon atom.
In
the activated terminal acetylene, carbon atom bearing a hydrogen tends
to
be trans
to
NO
ligands probably
owing to the
steric
interaction
193
between the phenyl ring of central phosphine and the alkyl group of
acetylenes.
NMR and
NMR spectra data are consistent with this
conclusion. However, as in the phenylacetylene case where *H and
NMR data contradict each other, the possibility of isomerization through
rotation
many
about the M -acetylene bond*62c^ which has been observed in
cases,
during
the
accumulation
of
NMR data cannot be
excluded. From the view of steric interaction between the phenyl ring
of the central phosphine and the alkyl group of the T) 2 -acetylene,
structure
where
the
carbon
the
atom bearing a hydrogen lies cis to the
central phosphine (in structure B) is expected to be more stable.
range of quartemary carbons of
The
r| 2 -acetylenes falls in the range for
2 e ' donor acetylenes proposed by T em p lcto n ^a which seems reasonable
from the fact that NO appears to be linear as shown by v n o
in the IR spectra.
(~1700 cm‘ l)
In the activated internal acetylene case, the fact that
q 2 -aCetylene occupies equatorial plane is clearly shown in the 13C NMR
spectrum.
Acetylene
methyl
carbons
and
carbonyl
carbons
are
not
equivalent as expected and chemical shifts of acetylene and carbonyl
carbons trans to central phosphine appear downfield rather than cis to
the central phosphine.
that linear NO
This might be explained by considering the fact
shortens the trans
ligand-metal distance
(vide
supra).
Therefore, acetylene carbon trans to NO should have more sp2 character
than that cis to NO, and the chemical shift of this carbon should be
upfield (in 1 3 c NMR spectra, sp2 carbon peaks appear upfield relative to
sp carbon peaks).
In the nonactivated internal acetylene reactions, the
assignments of the products are not easy.
For the diphenylacetylene
case, there is a well resolved triplet (2 jp .jj= 6 .3 Hz at 4.54 ppm).
Since no
acetylenic C-H is available, the origin of this peak is questionable.
This
194
raises questions about the assignment of q 2 -acetylenic complex.
Also
integration in the proton NMR indicates no phenyl ring from acetylene
in the coordination sphere.
This is confirmed by
NMR.
In the IR
spectrum, strong NO stretching peak is observed at 1840 cm‘ 1 and some
side peaks assignable to q 2 -acetylene
are also observed.
elem ental
best
analysis,
the
product
C 2 H 2 )(N O )(C y ttp )](B F 4 )3 .
is
T e m p le to n 2 8 7
form ulated
From
as
the
[R u (q 2 -
reported that 5H acety len e can
go up to 4.49 ppm in fac-W(CO)3(d p p e)(q 2 -CHCR) which contradicts the
7-13 ppm range reported elsewhere.2^ * 5 Therefore,
data support this formulation.
to
this product which
does
not
have
any
the
spectroscopic
However, the reaction pathway that leads
involves
oxidative
addition
precedent
exam ple,
and
o f phenylacetylcne
there
is
not
enough
experimental data such as C-H correlation to prove this pathway and
this
product.
form ulated
elemental
as
For
the
diphenylbutadiyne
case,
the
product
is
best
[Ru(C(Ph)CHCCPh)(NO)(Cyttp)](BF4)2 on the basis of the
analysis, but not enough spectroscopic data to support this
formulation is available and no conclusive decision can be made.
(i)
R eactio n s
D etailed
betw een
investigation
[R uH 2 ( N O ) ( e t p ) B F 4
was
made
only
for
and
the
A cetylene
reaction
[R u H 2 (N O )(etp )]B F 4 and dimethylacetylenedicarboxylate.
NMR data, the following structures are proposed.
between
Based on the
Fig. 68. 3 ip { iH } NM R S pectrum o f [R u (T i2 -(C C 0 2M e )2) ( N 0 ) ( C y ttp ) ] B F 4 in CD2C12
T
-t
H.O
-»
— r~ i
7.5
'T
i
i
t
|
7.0
6.5
t
6.0
1 1 1 i~ r
5.5
TI
5.0
r
» I 1 '
4.5
r ~T" l
4.0
PPM
»
1 !' 1 1 11 I * 1 ' 1 I '
3.5
3.0
2.5
1 'T * 1 1 1 J 1
2.0
1.5
T
I '” T
1.0
196
Fig. 69. iH NMR Spectrum of [Ru(ti2-(C C 0 2 M e )2 )(N 0 )(C y ttp )]B F 4 in CD 2 C I 2 a t 250.133 MHz
197
*tp**
Jl
-I ...-
(/Ai
*—
l-l.
'n-Alkyne
JJl
1 60
ISO
1 40
130
j l
**r"
1 20
1 10
10 0
90
PPM
70
60
SO
j
ww UwrUfAw
40
30
20
Fig. 70. 13C{!H } D E P T N M R S p e c tra o f [R u (ti2( C C 0 2M e ) 2) ( N O ) ( C y ttp ) ] B F 4 in CD 2C12 a t 62.896 M Hz
r~
~T~
3000
ICCO
1500
-500
cm-I
* measured as % transmission.
198
Fig. 71. IR Spectrum o f tR u (ti2-(C C 02M e )2 (N 0 )(C y ttp )]B F 4 in Nujol Mull
199
n+
PPh
PhP:
P P h 2:
or
: r u.
CN1
B
(96)
H owever,
since
[RuH2 ( N O ) ( e tp ) ] B F 4
is assumed to have a similar
structure to A and this reaction occurs very fast, there is no reason to
assume the structure change occurs.
favorable.
In
this
phosphines
sh ifts
complex,
upfield
Therefore, structure A seems more
a doublet
corresponding
sig n ifican tly
rela tiv e
complexes while the triplet shifts downfield.
to
to
the
the
alkenyl
If one assumes the trans
effect of NO is greater than that of alkenyl and ti2-acetylene
and
the strong trans ligand to shift the phosphorus peak upfield,
result can be explained.
wing
causes
the above
Also coupling constants in the r i2 - a c e ty le n e
complex are almost half of those of the alkenyl complexes. A similar
trend was observed in the Cyttp case.
This trend cannot be explained
simply because there are changes in the charge of the complex and the
ligand ( for the etp case, positions of ligands also change).
no
reasonable explanation is
available.
In the
*3 C
At this point,
NMR
spectra,
acetylenic methyl and carbonyl carbons are not equivalent as expected
and acetylene moiety acts as a 2-electron donor based on the chemical
200
shift of acetylenic c a r b o n s . ^ 3
in the IR spectrum, overlap of NO and CO
stretching peaks makes it difficult to assign those peaks, but based on
the IR peaks in the case of pheriylacetylene ( v ^ o ; 1790 cm‘ 1), a higher
frequency is assigned to v n o .
intense
and
broader
phenylacetylene
and
than
Also the fact that VNO is usually more
vco
supports
this
l,4 -d ip h en y l-l,3 -b u tad iy n e
assignment.
For the
reactions,
sim ilarity
in the 3 1 p NMR spectra dictates assignment of these products as t|2 acetylene complexes.
In the case of diphenylbutadiyne reaction,
possibility
cannot
including
of
dim er
Mass Spectroscopy
be
excluded
or conductance
to determine the structure conclusively.
and
further
the
investigation
measurement are needed
I
Table 20. 31P and *H NMR p a ra m eters for [R u(rj2-a c e ty le n e )(N O )P 3 ]B F 4
p3
Cyttp
etp
A c e ty le n e
31p NMR
S o lv e n t
*H NMR
8P c e n t e r
8P w i n g
2Jp p
8H a c e t y l e n e
2J p h
11.09
6.98
31.9
6.1(d)
22.8
CHCCOMe
8.22
8.72
27.4
8.81(m )
CHCCO2R
8.94
7 .7 2
29.3
8.06 (q ,b ro ad )
(MeC02C)2
4.85
7 .7 0
30.1
2
(MeC02C)2
106.21
52.58
8.3
3
PhCCH
114.86
57.66
7.6
111.14
54.95
7.9
PhCCH
PhCCCCPh
CD2CI2
A cetone
O th e r s
8M e2.64(s)
1.6
1
1. 5(OCH2); 4.34(q), 8(CH3); 1.35(t), 2j h h =7.1H z
2. 5(M e);3.92(s),3.91(s)
3. 8(Me);3.82(s), 3.73(s)
* Chemical shifts and coupling constants are measured in units of ppm and Hz.
NJ
o
Table 21. 13C NMR and IR p aram eters for [R u(r|2-a c e ty Ie n e )(N O )P 3 ]B F 4
Pa
Cyttp
IR
v(NO) v(CC)
v(CH)
1690
1785
3120
192.6(s)
1710
1840
3120
1660
166.3(s)
1700
1780
3110
1680
1730
1805
1690
1750
1830
1700
PhCCH
1790
1830
PhCCCCPh
1710
18 6 0
PhCCH
CHCCOMe
CHCC02Et
(MeC02C)2
etp
13C NMR
A c e ty le n e
(MeC02C)2
SCO
SC acetylene
2Jp c
113.5(d)
14.3
87.3(d)
14.5
97.5(d)
18.5
131.6(d)
19.6
117.2(d)
16.9
90.4(d)
16.0
119.2(d)
23.5
166.6(d)
108.8(dt)
13.2,4.8
161.2(s)
125.3(d)
24.5
163.8(s)
100.8(td)
9.4,4.6
161.3(d)
2Jp c
8.9
v(CO)
6.4
* CD2 CI2 is used as a solvent throughout the 13C NMR experiment and IR spectra are taken in Nujol Mull.
* Chemical shifts, coupling constants and stretching frequencies are measured in units of ppm, Hz and o
cm-1, respectively.
10
I
u,
1
'
I
115
1
1
1
1
I
110
1
1
1
1
I
105
1
1
1
1
1
100
1 T "'
■ I
95
I
I
I
1
I
90
I
■ I
I
I
S5
■
I
I -» -1
1
BO
PPH
I
< T -|
75
I
I
I
I
I
70
I
'
I
1
I
65
I
I
I
■ 1
60
I
I
I
I
I
55
I
I
1
-I "I
50
■ 1 -1
I T
I
T
l" 1
45
203
Fig.72. 31p{lH} NMR Spectrum of [Ru(T|2-(C C 0 2 M e )2 )(N 0 )(e tp )]B F 4 in CD 2 C I 2 a t 101.252 MHz
I
' T "1
I “I
| 'I
8.0
1
I
7.5
»' I
| 'T
7.0
f
I" > |" 'I
6.5
I 1I
I ■"[
6.0
I "T
T' 1
I T
I| T
5.5
A
1
1
l T - T- I
5.0
1~ I
I ■
I 1 111I
4.5
4.0
PPM
i—1
3.5
i"» » » »
3.0
2.5
i -» i - r l f
2.0
in
« |
1.5
i
1I
1.0
' > '
1I 1111I 1
.5
0.0
204
Fig. 73. 1H NMR Spectrum of [Ru(Ti2-(C C 0 2 M e )2 )(N 0 )(e tp )]B F 4 in CD 2 C I 2 a t 250.133 MHz
205
Lee CHI ONLY
_________________________________________ I
LEC CH 2 ONLY
\
_____________________________________.
tee
I
cm o n ly
cee c j 3 ea
60
20
Fig. 74. 13C { 1H} DEPT NMR S pectra of [RuOi2(C C C >2M e)2)(N O )(etp)]B F4 in CD 2 C I 2 a t 62.896 M Hz
Oxidative
1.
Addition
Reactions
of
RuH(NO)P 3
206
I n t r o d u c tio n
Collman288
defines " oxidative addition reaction" as the term
used to
describe reactions in which a group, A-B, adds to, and thus oxidizes, a
m etal
com plex.
In
th ese
reac tio n s,
m etal
com plexes
behave
simultaneously as Lewis acid and base. Since these reactions r e q u i r e ^ 9
a) nonbonding electron density on the metal atom and b) coordinatively
unsaturated
metal
coordinate
d® or d*0
o r
^ 1 0
they
transition
are
generally
metal
found
complexes.
in
There
4-
or
are
5-
many
reviews available and some of them are specialized in
l i t c r a t u r c 2 8 6 , 2 8 9
^ 8 2 8 6
complex,
transition
metal
c o m p l e x e s 2 8 9 g
The similarity between
oxidative addition of covalent molecules to unsaturated transition metal
complexes
and
chcmisorption
o f these
molecules
on
transition
metal
surfaces is already recognized. In the several homogeneously catalyzed
processes
such
as
hydrogenation
and
hydroform ylation,
oxidative
addition is a key step in the mechanism. It is also found that the
tendency
for d^
complexes
to undergo
oxidative
addition
reactions
depends on the nature of the central metal atom and other coordinated
ligands. The tendency for d® complexes to form oxidized adducts of d^
configuration
increases with descending a triad or passing from
right
to left within group VIII. Moreover, it is well recognized that electron
donating ligands enhance the tendency for metal complex to undergo
oxidative addition
r e a c t i o n . 2 9 0
linear NO group and formally
Since
they
oxidation
are
electron
rich
a s discussed before, RuH(NO)P3 have a
0
oxidation state
from
chelating
state and 5-coordinate, it is expected
and d^ c o n f ig u r a tio n .
triphosphines
and
low
that oxidative addition
207
reactions would occur.
In 5-coordinate d® complexes, oxidative addition
reaction takes place in two discrete steps, (equation
^ j_
5f
+
97
)
-L
8-
A— B
B
B'
✓IS
✓N
(97)
In
this
pathway,
reactions.
the
However,
first
step
another
is
quite
pathway
for
sim ilar
with
5-coordinate
the
acid-base
complexes
to
undergo oxidative addition is available via prior dissociation of a ligand
to form a more reactive 4-coordinate complexes. Dissociation o f a ligand
may be induced by heating or irradiation. Therefore, some reations of 5c o o r d in a te
d^
com plexes
req u ire
p h o to
rad ia tio n
or
high
te m p e ra tu re .291
2.
O xidative
a.
W ith
A ddition
R eactions
of
R uH (N O )(C yttp)
H alogens
R eactions
between
RuH (NO )(Cyttp)
and
halogens
(
X2
) produce
[R u X 2 (NO)(cyttp)]X. The amount of halogen used in this reaction does
not change the product at all; 1 equivalent of X2 produces exactly the
same product as does excess of halogens. In this regard, it is no wonder
that yield of these reactions are approximately 50 % when 1 equivalent
amount of halogen was used. The fate of half of starting materials was
not
investigated.
immediately
from
However,
the
since
these
products
are
precipitated
out
m other benzene
solution,
the
rest o f starting
208
m aterials
are
fo m u latio n
probably
suggested
present
above
intact
is
in
the
filtered
supported
by
solution.
the
The
co n d u ctiv ity
measurement. It is rather surprising not to isolate [RuHX(NO)(Cyttp)]X
which is a most probable product of initial addition. Considering the
instability of [RuH2 (N O )(C y ttp )]B F 4 , it is assumed that initial adduct is
unstable
toward
reductive
elimination
of
HX.
The
expected
product
should be RuX(NO)(Cyttp) instead. These complexes are expected to have
linear NO group and d^ configuration from the NO stretching frequency
in the IR spectra( vide
infra ) Therefore, these are expected to be
vulnerable to oxidative addition again. Addition of another molecule of
halogen would produce the final product, [RuX2 (NO)(Cyttp)]X. These are
summarized in
the
following proposed pathways.( eq.
P
r-.
98 )
+
i .-- x
X"
(98)
209
Equilibrium
between
[RuHX(NO)(Cyttp)]X
and RuX(NO)(Cyttp) can
be
easily rationalized by the fact that HX is a good oxidative addition
reagent, but insolubility o f [RuX2 (NO)(Cyttp)]X greatly favors the shift
of equilibrium toward RuX(NO)(Cyttp). Also, many examples o f stable
complexes of [RuL4HX]292 support that [RuHX(NO)(Cyttp)]X is a possible
intermediate.
Moreover, reaction
between
can produce the product as well.
in the reaction between
[RuHX(NO)(Cyttp)]X and HX
Similar reaction product was reported
Ir(NO)L3and 2 equivalents of H C lJ® ^
3 1 p an(j
NMR spectra suggest that Cyttp occupies meridional geometry and
NO is trans to the central phosphine and halide ligands are trans to each
other because the ipso carbon of the wing phosphine shows a triplet,
and
the
triplet occurs upfield
from
the doublet in
the
31 p
NMR
spectrum. However, the reason why only the trans isomer is produced is
not clear. In the reaction product with
1 equivalent of X2 , a small
amount of impurity ( Br2, 5.83(d), 1.5(t)*,Jpp=22.6 Hz; I2 , 1.74(d), -6.10(t),
Jpp=22.2 Hz, * , obscured) was found in the 3 1 p
NMR spectra. The
possibility o f cis and trans isomer is removed on the basis of the same
pattern ( triplet is upfield from doublet ) in the 31 p NMR spectra. Since
there is no hydride peak in the
^H
NMR
and
the
possibility
of
RuX(NO)(Cyttp) is dismissed by 3 Ip NMR, there might be an equilibrium
between 5 and 6 coordinate complexes where 6 coordinate complexes are
favored.
IR
stretching
frequencies
of
NO
in
the
iodo
and
bromo
complexes show that iodine is a good n electron donor as expected,
b. W ith
These
AIkyl( o r
reactions
Acyl ) halides
have been
widely
used
to
synthesize
alkyl
or
acyl
c o m p le x e s. 108,293 Moreover, alkyl migration to carbonyl ligand after
initial alkyl addition to produce acyl
h a l i d e ^ 9 3 b o r
reverse reaction of
— I—
-7
-0
-9
-10
-11
n
-12
1--------1--------1—
-13
PPM
-14
-15
-16
-17
-18
—I—
-19
Fig. 75. 31p{lH } NMR Spectrum of [R uI2(N O )(C yttp)]I in CD2C12 a t 101.252 MHz
I
2000
1500
IOOD
211
* measured as % transmission.
Fig. 76. IR Spectrum of [R ul 2 (N O )(C yttp)]I in N ujol M ull
SCO
1000
SCO
cm' 1
* measured as % transmission.
Fig. 77. IR S p ectru m o f [R uB r2(N O )(C y ttp )]B r in N u jo l M ull
213
th is !8 ,2 2 a
involving
Were
this
also
type
observed. One
of
production o f acetic
reactions
is
of the
the
acid using rhodium
most
famous
M onsanto
reactions
process
for
the
j n this process,
c a ta ly s ts .^ 9 4
oxidative addition of Mel is the rate dctermininng step. Mechanism of
oxidative addition reactions of alkyl halides spans S n 2 mechanism
free
radical
chain
and
was first proposed by
nonchain
mechanism.
The
or
form er mechanism
He noticed that kinetic order and the
H a lp e m .2 9 5
activation parameters of reaction of Mel with trans-[IrCl(CO)(PPh3 )2 ]
are quite similar to those obtained from the reactions of tertiary amines
with alkyl halides which go through a highly polar activated complex.
This
alkyl
mechanism
halides
requires
and
the
some
inversion
reactions
However, latter mechanism
cationic
9 6
confirm ed
this
for
chiral
p h e n o m e n o n .2
in distinguishing between
in some cases primarily
in te r m e d ia te s .2 8 9 c , 2
configuration
9
6
is also important in many other reactions
and there have been difficulties
mechanisms
of
owing to
failure to
these two
isolate the
Recent success in isolation or observation of
i n t e r m e d ia te s 2 9 7 ,2 9 8
clearly favors S n 2
mechanism
in some
reactions. In this research, however, the expectation o f alkyl or acyl
com plexes
could
not
be
achieved
and
only
corresponding
halide
complexes were obtained. Benzoyl chloride ( 1 equivalent ) and benzyl
chloride react with RuH(NO)(Cyttp) to produce RuCl(NO)(Cyttp) very fast
w hile
m ethyl
io d id e,
phenyl
iodide
and
d iio d o m eth an e
give
RuI(NO)(Cyttp), and cyclopropyl bromide yields RuBr(NO)(Cyttp) slowly.
Excess
of
benzoyl
chloride
[ R u C l2 (N O )(C y ttp )]C l.
31P
produced
NMR
the
spectra
com plex
of
fom ulated
RuI(N O )(Cyttp)
as
and
RuBr(NO)(Cyttp) are similar to that of isomer B of RuCl(NO)(Cyttp) ( TBP
geometry ) and this suggests that these complexes have TBP structure
214
with linear NO group. NO stretching frequencies in the IR spectra ( see
Table 22 )are almost the same as that of RuH(NO)(Cyttp) where NO is
linear, and this strongly supports the above assumption. In the reaction
with
excess
confirm ed
benzoyl
by
the
chloride,
reaction
pathway
with
through
1 equivalent
RuCl(NO)(Cyttp)
and
separate
was
reaction
between RuCl(NO)(Cyttp) and excess benzoyl chloride. These reactions
also show that the initial adduct [RuHR(NO)(Cyttp)]X is not stable toward
reductive elimination,
and the
fact that only
one
e x a m
p l e ^
2
where
both hydride and alkyl ligands are present is known to date strongly
supports this. The reaction rate to produce RuI(NO)(Cyttp) is observed in
the order of CH2 l 2>McI>PhI which is good accordance with that reported
else w h e re .288
c.
W ith
Acid
halides
Many hydride complexes are known to react with acid halides to give
halide complexes2^ 2 por example, RuH2 (N 2 )(P P h 3)3 and [Ru(PPh3)4 H] +
react with HC1 to produce RuCl2 (PPh3) 3 , while Ru(PPh3 )2 (P F 3)2 H 2 gives
R u (P P h 3 ) 2 (P F 3 ) 2 C l2 . In this research, general pattern described above
is followed but the type o f products is dependent on the amount of acid
halides as seen before in case of benzoyl chloride. In the series of
R uX (N O )(Cyttp)
triphosphine
in
and
the
[RuX2 (NO)(Cyttp)]X, the chemical shift of the
3 i p nm r spectrum
is sensitive
to the nature of
halide ligand. Generally, chemical shifts of the triphosphine go upfield
with descending the group. This represents the n
electron donor ability
o f halide ligand. However, no reasonable explanation why the doublet is
more
sensitive
in the
series
o f RuX(NO)(Cyttp)
cannot be
proposed
Surprisingly, NO stretching frequency does not reflect this trend very
well.
This
m ight
be
due
to
cationic
character
in
the
series
of
25
~r~ ~1— —r '
24
23
22
—I— ~T~
21
20
I—
19
I
16
I
17
~~l— ~l—
16
15
—
j—
14
PPM
I
13
I
12
~r~
ll
10
Fig. 78. 3 l p { l H } NMR Spectrum of [R uI(N O )(C yttp)] in C6D 6 at 101.252 M H z
I
“t—
.2000
T
T
T
T
—t—
T
T
i-
1000
ISOO
CAT'
* m easured as % transm ission.
216
Fig. 79. IR Spectrum of [R uI(N O )(C yttp)] in N ujol M ull
217
[ R u X 2 (N0 )(Cyttp)]X, but no appropriate explanation
sensitivity of NO stretching frequency to the
for the
lack of
change of electron density
on the metal atom in the series of RuX(NO)(Cyttp) is available. However,
in this series, dependence of NO bonding mode on the subtle change of
electronic density
on the metal ceter can berecognized. On descending
down the group,
TBP structure with linear
already
seen
in
the
density drives to
structure
NO group is favored. As
o f RuH(NO)(Cyttp),
change the structure
increased
electron
but not to bend the NO group.(
vide supra ) Meridional geometry of cyttp throughout the series was
confirmed by
summarized
NMR spectra. The proposed
in
equation
99.
The
final
step
reaction pathways are
involving
the
reaction
between coordinatively saturated 6-coordinate hydride complex and acid
is
frequently
observed
R uH 2 (N 2 )(PPh3 )3 .
in
the
6-coordinate
hydride complex
such
as
—
,------------------------------- 1---------------------- 1-------------------------- 1--------------------- 1
------------------------------------- 1---------------------------- 1--------------------- 1---------------------------- 1------------------------------ 1
-----------------1-------------------------------- 1
------------------------- 1
------------------------1
------------------------------ [—
26
25
24
23
22
21
20
19
16
17
16
15
14
13
12
PPM
218
Fig. 80. 3 lp { lH } NMR Spectrum of [RuB r(N O )(C yttp)] in C6D 6 at 101.252 MHz
!
1500
1000
* measured as % transmission.
219
Fig. 81. IR S p ectru m o f [R uB r(N O )(C yttp> ] in N ujol M ull
220
d.
With
Carboxyiic
Acid
As already mentioned in Chapter
two
flexible
com plexes
ligands
and
involving
2 ,
preparation of a complex containing
investigation
possible
mutual
of
the
properties
interchange
of
of
donor
these
abilities
between these two flexible ligands are one of the major objects of this
research. Only one such
e x a m
containing NO ligand(
p l e ^ 8
R
u
( N O ) (
t
| 3 -
a lly l)(P P h 3)2 ). except dinitrosyl complexes, is reported to date but other
com plexes
containg
carboxylate
ligand
com plex
oth er
have
m entioned
flexible
been
before,
ligands
such
reported.299 Also,
dissociation
of
in
as
n itrate
the
and
allylnitrosyl
triphenylphosphine
is
observed and true intramolecular mutual exchange of donor abilities is
not
reported
tendency
to
coordination
this
rare
yet.
However,
dissociation,
sphere
since
introduction
containing
phenomenon.
In
chelating
this
of
triphosphincs
flexible
triphosphine
m ight
regard, complexes
have
ligands
help
to
containing
less
to
the
observe
NO
and
carboxylate ligand are one of the top candidates for this purpose due to
its multidentate abilities as reported by Oldham.300 There are several
literature reviews covering carboxylate
biscarboxylate
of two
A lthough
no
ligands
and some
actually show exchange of bonding modes
c o m p l e x e s 3 0 2
carboxylate
c o m p l e x e s 2 9 2 , 3 0 0 , 3 0 1 ?
( mono
m onocarboxylate
and
bidcntate
com plex
shows
bonding
fluxional
modes
)
behavior
involving exchange of mono and bidentate bonding modes, both forms
are
observed
in
the
m ononuclear
c o m p l e x e s . 2 9 2
has been already
recognized that carboxylate complexes are usally catalytically active303,
and
R o b i n s o n 3
0 4
attributed
this
fact
to
the
intrinsic
coordination
properties of carboxylate ligand, moderate stability with relatively high
221
lability. Therefore, the possiblity of a potent catalyst of this system
where
NO
Preparative
and
carboxylate
methods
ligands
co-exist
to introduce carboxylate
of halide complexes with alkali metal^O^c
oxidative
c o m
addition
p l e x e s ^ O G
a c i d .3 0 7
co m p lex es
is
o f carboxylic
and
reactions
Generally, the
clean ly .
acid
to
worth
ligand
reactions
d& or d^ ® transition
complexes
last method is known
in
include
or sjjver carboxylates305j
of hydrido
T h erefo re,
investigating.
th is
with
to yield
research ,
metal
carboxylic
carboxylate
reac tio n
of
hydridonitrosyl complexes with carboxylic acid is chosen to synthesize
th e
c a rb o x y la to n itr o s y l
c o m p le x e s.
3 1p
NMR
sp ectra
of
carboxylatonitrosyl complexes arc similar to that o f RuCl(NO)(Cyttp), but
isom er A
type
complexes
are
greatly
favored.
In
other
words,
SP
stucture with bent NO group is favored over TBP with linear NO group.
Therefore,
it is temporarily
donor ligands favors
concluded
that highly
electronegative
n
SP structure with bent NO group and this trend is
also observed in the series o f [Ru(NO)X(CO)(PPh3 )2 ] ^ ^ a where NO
stretching
frequency
decreases
with
increasing
electronegativity
difference is not large. Again, sensitivity of the doublet in the 31p
but
NMR
to the change of electron density on the metal center is demonstrated in
the series of [Ru(0C(0)R )(N 0)(Cyttp)]. Chemical shift of the doublet (
wing
phosphine
of
Cyttp
)
moves
upfield
with
increasing
electron
withdrawing ability of the alkyl group. The nature of bonding modes of
the
carboxylate
ligand
is
usually
determ ined
by
the
positions
of
symmetric and asymmetric stretching frequencies o f OCO group3®7a,308
Chelating carboxylates have values of v(O C O )asym and v(O C O )sym close
to
those
found
in
the
corresponding
carboxylates have v (O C O )a sym
free
ion
whereas
monodentate
at substantially higher frequencies and
222
thus give larger values of [v (O C O )aSy m - v ( O C O ) Sym]- 111 this series of
carboxylatonitrosyl
c m 'i
com plexes,
the
difference
values
are
around
140
which is on the borderline of the empirical criterion suggested by
R o b in s o n .3 0 7 a
h a lo n itro s y l
monodentate
formed,
However, similarity
and
of 3 1 p
c a rb o x y la to n itro s y l
bonding mode.
metal-oxygen
bond
Moreover,
distance
NMR
spectra
co m p lex es
if chelating
trans
to
NO
between
su p p o rts
bonding
group
elongated due to strong trans effect of bent NO group^
the
mode is
should
be
and interaction
between metal center and oxygen atom is weakened. In consequence,
the chelating mode is not favorable in these complexes. NO stretching
frequencies in the IR spectra ( around 1460 cm"* ) also indicate bent NO
group and support SP
geometry with bent apical NO group. Carboxylate
group should be trans to central phosphine because the triplet occurs
farther downfield than the doublet. Meridional geometry o f Cyttp was
confirmed by
NMR spectra. Therefore, the following structure is
assigned to these complexes. (
equation 100 )
O — C— R
( 100)
U nfortunately,
abilities
in
between
a c e ta to n itr o s y l
these
NO
com plexes,
and
co m p le x ,
no
carboxylate
a n o th e r
mutual
ligand
exchange
is
s y n th e tic
of
observed.
For
p ath w ay
[RuH 2 (N O )(C yttp)]B F4 and sodium acetate proves to be also feasible,
e.
W ith
P henols
donor
the
u sin g
40
1~
38
-J36
~r
34
"T~
~r
32
30
T“
28
~T~
26
t
24
PPM
“T"
“T”
22
20
X
T“
18
"7“
16
X
“T
14
x
T~
12
~r
10
X
T
8
223
Fig. 82. 3 l p { l H } NMR Spectrum of [R u (0 2C C H 3)(N 0)(C yttp)] in C6D6 a t 101.252 MHz
1 T " 1 ■~r ~ T '
8 .0
|
7 .5
1 '
T '
I
7 .0
*
1
'
i
1
—i
6 .5
i
i—i
f~ i—i—!—i—|— i—i—i— !—]—i—i—i—i—|— i—i—i—i—j—»
— i—r—r—|—r—r—i—i— p —
i—r—i— i— j—i— i—i
6 .0
5 .5
5 .0
4 .5
4 .0
PPH
3 .5
3 .0
2 .5
t
|
2 .0
i
t
v
i
|
1 .5
i -»- i
i
|
1 .0
i
i
i
i
|
t
i
i
i
.5
22 4
Fig. 83. 1H NMR Spectrum of [R u (0 2C C H 3 )(N 0 )(C y ttp )] in C 6D 6 a t 250.133 MHz
225
M* * * \m i
i
J * » n n * ,* y W h f * **** * * ,•& * *
A^O-u.
^-JU
OUMN0CYTTP * C H 3 C 0 0 H C 1 3 0 0
■ • r~ i ' ' ’ ■ ' ' I ' ' ' ’ 1— 1 ■ ■ ■
35
30
25
20
PPK
i • J■
15
' I '—'
10
~’~'
I *'•'■»—• |
5
0
Fig. 8 4 .13C { 1H} D E P T N M R S p e c tru m of
[ R u ( 0 2C C H 3)(N 0 )(C y ttp )] in C D 2C I2 a t 62.896 M H z
( A lkyl R egion
O nly)
1
1500
1060
Fig. 85. IR S p ectru m o f [R u (0 2C C H 3)(N O )(C yttp>] in N u jo l M ull
226
* measured as % transmission.
I
36
i
i
i
i
i
i
i
i
i
i
i
35
34
33
32
31
30
29
28
27
26
25
i
i
24
23
PPM
i
i
i
i
i
i
i
i
i
i
22
21
20
19
18
17
16
15
14
13
i---------- 1—
12
227
Fig. 86. 3 lP { lH } NMR Spectrum of [R u (0 2 C P h )(N 0 )(C y ttp )] in C6D6 at 101.252 MHz
11
I
T
10
I
38
“I
36
1-----1-----'-----1—
34
32
—I
30
i-----|-----1-----1-----1-----1-----1-----1-----1-----1-----1-----,-----1-----p28
26
24
20
18
16
—j-----1------ 1---1------ 1---1------1--- 1
14
12
10
8
Fig. 87. 31p{lH } NMR Spectrum of [R u (0 2C P h N 0 2)(N 0)(C yttp)] in C 6D 6 a t 101.252 MHz
22 8
PPM
22
229
Wide use o f metal alkoxides ranging from catalysts to precursors of
metal oxides, glasses and c e ra m ic s3 0 9 h as propelled extensive studies on
the alkoxides of various metals. However, investigation of group VIII
metal alkoxides started very recently partly because of the belief that a
hard base such as alkoxide is not compatible with soft metal acids.^ * ®
Recently, metal alkoxides are proposed as a model of metal oxides^ * *
w hich
are
im portant
in
the
area
of
heterogeneous
cataly sis.
Considering the fact that many group VIII metals and metal oxides have
been shown to be effective catalysts in several reactions, understanding
of the properties of alkoxides of group VIII metals could give some
insight on metal oxide catalyzed reactions. Moreover, recently reported
chemistry of group VIII alkoxides contains many interesting reactions.(
Ir; J. D. A tw ood^l2> pj; jj.E. Bryndza^l^ and some other g r o u p s ^ R h ;
P .M .
M a iltis^ lS
) As a result, research interests in the second and third
row group VIII metal complexes are increasing and lots of papers in
this field have been published for the past several years. Despite of this
trend
in this
field,
synthesis
and
investigation
of the
chemistry
of
ruthenium alkoxides are rare. According to G rey316, this might be due
to
intrinsic
ruthenium
reversibility
complexes.
p latin u m
m etals^ 17
A
of
reaction
recent
shows
with
review
that
all
on
alkoxide
the
reported
ligands
alkoxy
in
complexes
ruthenium
the
of
alkoxide
complexes are either binuclear or polynuclear. Beyond the coverage of
this
found
review,
three
elsew here.
examples
However,
o f mononuclear ruthenium
C p * ( P M e 3 ) 2 R u ( O H )3 18
alkoxides
are
js actually a
hydroxide,
R u H ( O C ( H ) ( P h ) C F 3 ) ( P P h 3 ) 3 3 19 is questionable due to lack of
d e ta ile d
s y n th e tic
p ro c e d u re
[P P h 4 ][R u (catech o l)3 ]3 H 2 C )3 2 0
and
a n a ly s is
d a ta ,
and
was characterized by IR spectroscopy
230
only.
Despite o f this
lack o f isolated
alkoxide complexes,
ruthenium
alkoxide complexes are frequently proposed as active intermediates in
the
catalytic
tertiary
processes
phosphines.
catalyzed
by
Hydrogenation
ruthenium complexes
o f k e to n e s ^ 1,
containing
a ld e h y d e s^ 1 a,b,c
and esters3 2 1 a,c,3 2 2 an(j dimerization of aldehydes^23 are among these
processes. In these processes, Grey 3 1 6
postulates the active catalyst
form for hydrogenation of carbonyl compounds
and
nucleophilic
character
inherent capacity
tertiary
to
o f the
hydrogen
react reversibly
with
as follows: 1. hydridic
atom
alkoxy
on
the
metal.
ligands.
2.
3. having
phosphines as stabilizing ligands for metal atom to minimize
the dispersal o f the negative charge of the complex. They also pointed
out that any factor which favors hydride transfer from the complex to
the
carbonyl
compounds
(
cationic
assistance, electron
withdrawing
groups on the ketone, nuclcophilicity of the hydride ) would make a
more
group
efficient catalyst.
on
the
alkoxide
alkoxide
ligand.
Among these
properties,
ligand m ight help
Moreover,
electron
to
electron
stabillize
withdrawing
withdrawing
the
property
resulting
through
n
backbonding o f anchoring ligand on the metal seems to be essential to
stabilize
the
com plexes.
alkoxide
M ost
ligand
alkoxide
as
seen
complexes
in
are
many
group
conveniently
VIII
alkoxide
prepared
by
replacing the halide with alkoxide ion, but insertion of ketone into M-H
b o n d 3 2 3 ,3 2 5
unsaturated
an(j oxidative addition of O-H bond of phenol to an
m etal
com plex326
were successfully
applied to produce
alkoxide complexes. Most ruthenium alkoxide complexes are believed to
be
unstable
hydrogens,
tow ard
and
P
hydride
transfer
when
usually
hydride
com plexes
are
p ro d u c t . 3 1 8 ,3 2 6 ,3 2 7
However, even reactions
alkoxides
obtained
as
have
a
p
final
with phenoxide or t-
231
butoxide
fail
to
produce
corresponding
since p
a l k o x i d e s . 3 2 6 , 3 2 8
hydrogen transfer can be limited by coordinative
s a t u r a t i o n ^
8 8 ( jn
t h e
complexes with a chelating triphosphine and NO ligands this process
can
be
effectively
blocked
owing
to
a
lesser
tendency
toward
dissociation. Moreover, as discussed before, strong trans effect of bent
NO ligand may limit the interaction between metal atom and p hydrogen.
Now,
in
this
section,
a new
method
to
prepare
the
rather
stable
ruthenium phenoxo complex is successfully introduced. Since phenol is
a weak acid, the synthetic method used to prepare the corresponding
carb o x y lato
com plex
can
be
applied
but
a
reactio n
betw een
RuH(NO)(Cyttp) and phenol fails to produce a clean phenoxide complex.
This
reaction
tem perature,
is
very
complicated
slow
at room
mixture
tem perature
resulted.
W ith
and
the
at
aid
the
of
reflux
external
proton source such as HBF4 , reaction products are not simple. However,
p-nitrophenol reacts immediately to produce a phenoxide complex. 3 1 p
NMR spectrum of this complex is similar to those of carboxylatonitrosyl
complexes but shifted downfield a little bit. This similarity shows that
phenoxides are bound through O atom and not the n ring system. This is
clearly shown by the *H NMR spectrum. In this spectrum, protons of the
phenoxo ring appear at 6.8 and 7.5 ppm, while in n -phenoxo
ring bound
complexes these resonances are known to shift
Also, there
u p f i e l d . ^ 2 8
are no characteristic six peaks in the range of 480-550 cm"* in the IR
spectrum. The possibility o f bonding through the oxygen atom of the
nitro group can be dismissed by the fact that no charcteristic peaks of
the O-H group can be found in IR and *H NMR spectra. A strong peak at
1110 cm- *, characteristic o f coordinated alkoxide group, supports this
conclusion. Also careful comparison o f the IR spectrum of this complex
232
with that of Ru(0 C(0 )PhNC>2 )(N0 )(Cyttp) shows that this peak is typical.
S tretching
frequencies
of
nitro
group
(1590
and
1300
cm"* ) is
characteristic for the noncoordinating nitro group, and coordination of
this group usually shifts these peaks to lower frequencies. This complex
is fairly stable in the solid state, but in dichloromethane it decomposed
to an unknown mixture in a day. The stability of this alkoxide complex
appears
to be due to the
phenyl
ring
cannot be
presence of the nitro and nitrosyl group on the
and metalatom,
prepared
through bridging
in
NO,
other
respectively,
systems
suggested
by
because
other
The
possibility
yet.
the
poor
alkoxides
solubility
o f dimer
cannot
be
completely excluded but NO stretching frequency in this complex ( 1495
c m '* ) , similar to those of carboxylato analogues, indicates that this is a
monomer. Also, mass spectrum of this complex support this formulation.
The
possiblity
excluded
by
coordination
o f a dim er through
the same
in
the
argument
bridging
applied
carboxylatonitrosyl
for
alkoxide
the
com plexes.
group
preference
In
can
be
for 5-
summary,
the
following 5-coordinate SP structure with the nitrophenoxo group trans
to the central phosphine is proposed, (equation 101 )
(101)
f. W ith NOBF4
T“
40
~T~
38
T
36
T
T “
34
"T~
32
T
“ I-
30
T
~T~
28
T
T“
26
"T “
24
“1“
22
PPM
T
X
“I”
18
X
~r~
16
X
"T “
“ I”
14
12
X
~T“
10
T
8
T
6
233
Fig. 88. 31P{lH} NMR Spectrum of [R u (0 P h N 0 2)(N 0)(C yttp)] in CD 2 C I 2 a t 101.252 MHz
-i IN T E G R A L
8 .5
8.0
7 .0
6 .5
6.0
5 .5
5 .0
4 .0
PPM
3 .5
3 .0
2 .5
2.0
0.0
234
Fig. 89. J H NMR Spectrum of [R u (0 P h N 0 2)(N 0 )(C y ttp )] in CD2C12 at 250.133 MHz
I
I
r
zcaa
r
r
T
T
1000
1500
T
t
500
Cm
* measured as % transmission.
235
Fig. 90. IR Spectrum of [R u (0 P h N 0 2)(N 0)(C yttp)] in N ujol M ull
236
This reaction was initially designed to investigate the electronic effect
on
the
bonding
modes
of the dinitrosyl
complexes and the possibility of
NO
in
the
exhaust
gas
groups
in the
5-coordinate
the catalyst for the removal of CO and
by
p rep arin g
R u(N O )2 (C y ttp )
ai»d
[R u (N O )2 (C y ttp )]2 +. To date, all 5-coordinate dinitrosyl complexes are
{ M ( N O ) 2 jJ*
and have one linear and one bent NO group but no
{ M ( N O ) 2 }*® complex is reported. From the MO analysis proposed by
E nem ark
and
{M(NO)2 } ^
favored,
F elth am ^
, it
is expected that
in the 5-coordinate
complexes, SP structure with a bent and a linear NO is
whereas
{M(NO)2 }® spans from SP to TBP with two linear NO
groups. Since neutral Ru(NO)2L 2 and M(NO)L3 (M=Co,Rh,Ir) are very
reactive
toward
oxidative
addition
reaction,
Ru(NO)2 (Cyttp) is
also
expected to be reactive but to a lesser extent owing to higher oxidation
state ( 0 ) compared with other complexes mentioned above. ( -2 and - 1,
respectively
to
date
b e tw e e n
) Unfortunately, this
probably
owing
to
RuH(NO)(Cyttp)
compound has not been
instability
and
to
decom position.
synthesized
Reactions
N -m e th y l- N - n itr o s o - p - to lu e n e -
sulfonamide( Diazald ) and Co(DMG)(NO) and Ru(NO)2(P P h 3>2 and Cyttp
give uncharactcrized mixtures. However, [Ru(NO)2 (C y ttp )][B F 4]2 can be
easily prepared by the reation between RuH(NO)(Cyttp) and NOBF4 . This
reaction is accompanied by the vigorous bubbling of gas. The nature of
this
gas was not investigated
but this
might be
NHO
(unstable)
or
mixture o f H2 and NO. Considering this, the following reaction pathway
was proposed. ( equation 102 )
237
f-P
s-P
I
,
-r u — H
CN^ |
V p
NOBF4
--------- ►
P*
1 +
^~P
I
~j 2+
NOBF4 P-*. I
' ^ R u — ISD
J
„
O N ^ j
V p
' ^ R u — -ISP
-NHO C N ^ I
V p
( 102)
At this point, the nature of the NO group is not clear because both NO
streteching frequencies
are rather high ( 1790 and 1830 cm"* ) in the
IR spectrum. If these two NO groups are linear, the angle between these
two
groups
can
be
calculated
by
the
following
equation. 149
This
equation is originally formulated for the carbonyl complexes but since
linear NO is isoclectronic with CO, there is no problem to apply this
equation to the nitrosyl complexes even though no such attempt has
been reported to date. However, if the nature of two NO groups are
different the validity of this equation is doubtful owing to a different
nature
of
the
dipole
vector
in
the
different
NO
group.
Anyway,
application of this equation shows that the angle between two NO groups
is 95 degrees.
^sym
^asym
2 r cos 0
2 r sin 0
2
c o ta n 2 0
(103)
R; Intensity of peak
0 ; angle between the two ligands
This is not the value as expected from the MO analysis ( around 120° )
for two linear NO groups in 5-coordinate complexes. Also, the chemical
shift difference between doublet and triplet (24 ppm ) in the 31 p
NMR
spectrum is comparable with that of RuCl(NO)(Cyttp) of SP structure. (
238
22 ppm )
while the coupling constant (35.7 Hz) is similar to that
of
RuCl(NO)(Cyttp) of TBP structure (37.5 Hz). However, since high positive
charge on the metal center clearly disfavors n
the
back bonding to lead to
bent NO ligand, TBP structure with two linear NO
tentatively
proposed.
linear NO groups
central phosphine
In this
structure, combined trans
groups is
effect o f two
may exert the same effect as if one of them is trans to
even
though
no
proposed formula is supported by
such
effect
is
reported
yet.
elemental analysis and conductance
measurement. An attempt to clarify the nature of NO group by ^ N
spectroscopy
failed
The
NMR
owing to nonconsistence between NMR and large
scale reactions between RuH(NO)(Cyttp) and HBF4 and N a ^ N 0 2 - In the
large scale reaction, unknown mixtures resulted every time. Moreover,
if two NO groups exchange positions, the nature of NO cannot be defined
at the room temperature and the question about the nature of NO group
requires low
temperature
^N
NMR which is time consuming.
Also,
considering the proposed reaction pathway, it appears to be difficult to
prepare 50%
enriched
sample;
thus, detailed mechanism
for exchange
may not be obtained. In the 31 p NMR spectrum, no sign of exchange was
detected and every peak is sharp. An attempt to grow crystals for X-ray
crystallography
failed
owing
to decomposition
in the
solution. 1 3 c NMR spectrum shows that Cyttp has
No
further
removal of
attempt
was
made
to
investigate
dichloromethane
meridional geometry.
catalytic
reactions
NO and CO with this complex. It will be also interesting to
reduce this complex electrochemically to produce Ru(NO)2 (C yttp).
In se rtio n
1.
of
R eactions
Introduction
o f C 0 2 -lik e
M o lecu les.
^ViiVv^WV*
_,---- j.
26
~r
24
T
20
T~
T~
16
16
~T~
14
~T~
12
PPM
T~
10
T
6
T
T
6
T
4
T
T
2
T
T
0
T
"1”
-2
T
T
-4
239
Fig. 91. 3 lp { lH } NM R S pectrum of [Ru(NO)2(C y ttp )] [B F 4 ] 2 in CD2C12 a t 101. 252 MHz
I
* measured as % transmission.
240
Fig. 92. IR Spectrum of [Ru(NO) 2 (C y ttp )][ B F 4 ] 2 in Nujol M ull
T a b le
22.
S p ec tro sc o p ic
o f O x id ativ e
A d d itio n
P ro d u c ts
31P NMR
P ro d u c t
R e a d ta n ts
C o m p le x A d d e n d u m
Br2
RuH(NO)(Cyttp)
D a ta
12
C o m p le x
PhCOCl.leq RuCl(NO)(Cyttp)
excess
SP wine
2J p p
so lv e n t
v(NO)
1.58
22.5
A cetone
1835
-1 6 .9 5
- 10.01
22.2
23.01
19.48
37.5
37.06
15.33
43.8
9.28
2 3 .4
9.36
39.0
B enzene
1600
22.56
35.7
CD2C12
1790,1830
15.40
37.1
B enzene
1605
SP cent er
[RuBr2 (NO)(Cyttp)lBF 4 -3 .1 9
[RuI2 (NO)(Cvttp)]BF 4
[RuCl2(NO)(Cyttp)]BF4 4 .0 6
c h 2i ,c h 2i 2 RuI(NO)(cyttp)
IR
2 0 .9 6
Phi
RuI(NO)(Cyttp)
PhCH2Cl
RuCl(NO)CCyttp)
NOBF4
[Ru(NO)2 (Cyttp)l[BF 4 l 2 -1.43
HC1, 1 eq
RuCl(NO)CCyttp)
1830
CD2CI2
1840
. excess [RuCl2 (NO)(Cyttp)]Cl
HBr, 1 eq
RuBr(NO)(Cyttp)
, excess [RuBr2 (NO)(Cyttp)]Br
2 2 .5 6
!
MeCOOH,li ;qRu(02CMe)(NO)(Cyttp: 35.07
11.59
44.3
2 1 .8 4
18.91
4 0 .4
R u(02CPh)(NO)(Cyttp) 35.53
12.33
44.3
2 1 .3 9
18.73
39.9
PhCOOH
p -N 0 2Ph-
Ru(02CPhN02)(N0)-
35.53
13.11
4 4 .2
GOOH
(Cyttp)
2 0 .3 9
18.14
38.8
p-N 02PhOF R u(0PhN 02)(N0)(Cyttp' 3 9 .0 0
16.76
4 5 .0
RuH(NO)(etp)l 4eCOOHe
R u (0 2CMe)(NO)(etp)
B enzene
1460a
1470b
c
CD2C12
1495d
108.55(br) 7 9 .1 9 (b r)
a.8(CH3); 1.55ppm, v(CO); 1550,1410cm*1
b. v(CO); 1565,1420 cm-1
c. too complicated to assign
d. v(Ru-O); 1110 cm*1
e. at 303K
* Chemical shifts, coupling constants and stretching frequencies are measured in units of ppm, Hz and
cm*1.
242
243
In
view
abundant
o f the prospect o f a shortage
of organic
carbon
sources,
CO2 has attracted much interest as a building block of organic
compounds. However, due to the high thermodynamic stability (
A G f° =
-94.254 kcal/molc ) and kinetic inertness o f CO2 . the activation o f CO2
cannot be fully achieved yet. Despite all the efforts described in the
recent
the chemistry for catalytic activation of CO2 is still
r c v i e w s 3 3 0 >
underdeveloped.
Among
the
reported
reactions
of
CO2 ,
insertion
reaction into the M-H, M-C, M-N, and M -0 bonds is important for organic
synthesis,
and
many
exam ples^ 31
are
reported.
Recent
mechanism
on the insertion of CO2 into the metal-alkyl bond show that
s t u d i c s 3 3 2
this reaction is dependent on the nature of the metal center, ligand and
alkyl
groups,
m aintained.
Contrary
and
that
From
to
this
recent
the
configuration
result,
concerted
progress,
early
of
the
alkyl
m echanism
sluggish
group
is
is
proposed.
developm ent
of
CO2
activation leads to the interest in coordination chemistry of CS2 and
sim ilar hctcroallcnes with transition metals, due to the fact that these
small
molecules
are
structurally
sim ilar to
CO2 and thus their metal
complexes can be regarded as model compounds for CO2 activation. With
increasing
interests
hctcroallcnes
has
in
been
this
w ell
field,
activation
r e v i e w e d . ^ ^ 3
of
These
CS2
and
related
review show that
insertion of CO2 into M-X (X=H,C,0,N) is limited to some transition metal,
especially to Mo or W, while insertion of CS2
and
heteroallenes is
reported for a wide variety of metal complexes. Insertion of CS2 and
heteroallenes generally results in the formation of a 4-member metallo
ring and X group moves to the center carbon atom^S 4
w hen X is
hydride, characteristic peak o f CH appears at ca. 15-8 ppm in the
244
NMR spectra, and a strong
peak at
ca. 1200 and 900
c m 'l , assigned to
v (C S 2 ), is generally observed in the IR spectra.
.
R u H (N O X C y ttp )
a. W ith CS2
This reaction proceeds very fast to produce Ru(SC(H)S)(NO)(Cyttp). This
complex was characterized by NMR and IR spectroscopy. In the
NMR
spectrum, a characteristic peak assignable to CS2 H hydrogen appears at
1 2 .0 4
ppm and no splitting is observed which means that the CS2H group
is not trans to a phosphorus
However,
a to m 3 3 4 g
distinction
between
dithioformate and dithioacid cannot be achieved by these data only. In
the 1 3 c NMR spectrum, carbon peak of CS2H appears at
this peak is split by
with
that
of
phosphine
the
and
para
this
because quarternary
Hz. The intensity of this peak
1 0 .4
carbon
clearly
carbon
of
shows
the
that
should show
(Nuclear Overhauscr Effect ) Also,
phenyl
this
ring
carbon
ppm, and
2 4 6 .1 2
is comparable
of
the
has
low intensity
central
a hydrogen
due to
NOE
^ Jp _ c value shows that these two
atoms are located trans to each other across the Ru-S
w hether
b o n d .3 3 5
the dithioformate group is bonded to metal via chelating mode or
by the
S atom only can be
In the
31P
NMR
determined by the 31 p NMR and IR spectra.
spectrum ,
phosphine peaks is
the
difference
between
the
center
and
wing
rather small ( 3 ppm ), and this indicates that the
center phosphine does not have any trans ligand. Thus, a 5-coordinate
complex.
In the IR spectrum, NO streteching appears
at
1 6 3 0
cm" 1
indicating linear NO group. Alas, no characteristic stretching band at
1200
c m" l
for
chelating
dithioform ate
group
is
observed
complex shows two strong peaks at 995 and 980 cm"* instead.
but
this
P a la z z i3 3 4 j
reported that S-bound dithioformate group shows strong bands at
1 0 5 0
I—
19
~1—
18
I
17
—!—
r~
15
16
T“
14
I
13
1
12
PPM
245
Fig. 93. 31p{lH } NMR Spectrum of [Ru(S2C H )(N O )(C yttp)] in CD2C12 a t 101.252 M Hz
IN TEG RA L
I
” £2
12.0
11.0
10.0
9 .0
B.O
7 .0
6.0
5 .0
4 .0
3 .0
a.o
o.o
PPM
246
Fig. 94. 1H NMR Spectrum of [Ru(S2C H )(N O )(C yttp)] in CD2C12 a t 250.133 MHz
fw p ^ W PS
260
240
220
200
160
" T ”
160
I....
""I'"'
120
"T "
100
80
"T"
60
• T"
40
"T ”
20
Fig. 95. 13C{lH} NMR Spectrum of [Ru(S 2 C H )(N O )(C yttp)] in CD 2 C I 2 a t 62.896 MHz
247
140
PPH
SCO
* m easured as % transm ission.
Fig. 96. IR S p ectru m o f [R u (S jC H )(N O )(C y ttp )] in
«
N u jo l M u ll
248
cm'1
249
and 930 c m 'l
above
in trans-PtCKq *- S 2 C H ) ( P P h 3 ) 2 , and this supports the
assignm ent.
coordinate
com plex
The
in
same
the
argum ent
for
carboxylatonitrosyl
the
preference
com plexes
of
5-
discussed
before can be applied here again. On the basis of these spectroscopic
data, the following structure is assigned to this product, (equation 104 )
S C (H )S ^ |
(104)
b. W ith PhNCO
This reaction is rather slow compared with the above reaction but it
appears to produce the same type of product, a formamido complex. In
the proton NMR spectrum, there is a peak at 9.29 ppm characteristic of
the formamido group. As discussed above, this complex is expected to be
a 5-coordinate, and whether this has a N-bound or O-bound formamido
group should be distinguished. From the extensive study of the strength
of M-X (X=H,0,N,C) bond by B c rc a w ^ l^ ^ js expected that Ru-0 bond is
preferred to Ru-N bond. This assignment is supported by the 31 p and IR
spectra. The trend shown in the 3 1 p NMR spectrum is similar to those of
carboxylato
and
phenoxonitrosyl
complexes.
A triplet
appears
further
downfield than a doublet, and the difference between these two peaks
(20 ppm) and the coupling constant ( 44.4 Hz ) are comparable. NO
INTEGRAL
9 .5
9 .0
8 .5
7 .5
6 .5
5 .5
5 .0
4 .5
3 .5
3 .0
2 .5
2.0
Fig. 97. 1H NMR Spectrum of [R u(O C(H )N Ph)(N O )(Cyttp)J in C6D 6 a t 250.133 MHz
250
4 .0
PPH
251
stretching frequency ( 1550 cm"* ) is also similar, and some peaks ( 1600
cm ‘ 1 )
assignable to C=N stretching frequency are found in the region
for substituted imines. ( 1600-1650 cm'* )52
the following structure
On the basis of these results,
is proposed for this complex, (equation
105 )
OC(H)NPh
(105)
c.
W ith
Several
were
Iso th io c y a n a te s
reactions
performed
reaction
with
to
phenyl,
investigate
o f isothiocyanates
into
p-tolyl
the
the
and
p-nitrophcnylisothiocyanatc
electronic
M-H
effect
bond.
on
the
insertion
U nfortunately,
these
reactions are not very clean, but in the case of phenylisothiocyanate,
rather pure complex is isolated and a thioformamido type produt can be
confirmed by
NMR and IR spectra. Typical thioformamido proton is
detected at 9.68 ppm in the proton NMR spectrum, and NO stretching
frequency
(
1620
cm "l
)
is
com parable
to
that
o f dithioform ate
complexes. Considering the fact that
sulfur shows better coordinating
ability
is
than
oxygen,
this
complex
expected
to
have
S-bound
INTEGRAL
I
g.o
8.0
6.0
5 .0
4 .0
3 .0
2.0
Fig. 98. *H NMR Spectrum of [R u(SC (H )N Ph)(N O )(C yttp)] in C6D(j a t 250.133 MHz
0.0
252
PPM
2 53
thioformamido
group.
C=N stretching
band
might be covered by the
broad, strong NO stretching peaks, but a strong peak at 1505 cm '* may
be assigned as v(C=N). However, this band might be due to aromatic ring
stretching.
31 p
dithioform ate
downfield
NMR
complex
than
the
spectrum
but
wing
the
shows
center
phosphine
second
phoshine
peaks,
order
peaks
which
dithioformate complex. Following structure is assigned
on the basis
of spectroscopic data.
(equation
is
spectrum
occur
as
further
reverse
in
the
to
this
product
title
of
insertion
106 )
PhNC(H )S'
(106)
d. W ith SO 2
Even
though
reactions
of
heteroallenes
this
reaction
heteroallenes,
is
discussed
sulfur
under
dioxide
is
the
different
from
other
s tr u c tu r a lly ^ ^ . This molecule is bent and has a lone pair
of electrons on the sulfur atom. Owing to this structural property, it can
behave as a Lewis base. However, it can also behave as a Lewis acid, and
this amphoteric nature was well reviewed in recent
chemistry o f sulfur dioxide
I i t e r a t u r e . 3 3 7
The
with transition metal complexes has been
accumulated rapidly primarily due to the fact that this unpleasant gas is
254
one of the major pollutants. The studies in this field are extensively
reviewed recently 3
3 7 ,3 3 8 f b ut
few examples o f insertion of S 02 into
very
M-H bond have been reported, while detailed mechanism study on the
insertion of SO2 into M-alkyl bond has been already
first indication of insertion o f SO2
an(j
R o b i n s o n ^ 4 0
reaction
between
p u b lish e d .3 3 9
The
into M-H bond was proposed by
1 claimed that the product of the
Y a m a m o to 3 3 4
RuH2 ( P P h 2 M e )4
and SO2
is a sulfinatc complex,
R u (S 0 2 H )2 (P P h 2 M e)3 . However, the first fully characterized example in
this category
between
only in
K u b a s 3 4 1
reported the unusual
K u b a s ^ 4 2
reaction
was published by
1985.
More recently,
metallo sulfonic acid prepared by the
Cp*Ru(CO)2H and SO2 . This product is believed to be
prepared via insertion
and oxygen transfer from
another molecule of
S O 2 , and crystal structure was reported. Now, in this section, synthesis
of
an o th er
m etallo
su lfo n ic
RuH(NO)(Cyttp)
and
trip let
further
appears
acid
by
th e
reac tio n
SO2 is reported. 3 1 p NMR spectrum shows that a
upficld
between the two peaks is ca.
than
a
doublet
but
the
2 0
ppm ). This indicates that SO3H is
bound through the S atom. The NO stretching frequency (
1630
cm '* ) is
to those found in the S-bound complexes. On the basis of the
literature, the weak bands
at
2 4 5 0
and
cm'* are assigned as v (O H )
1270
and 5(OH), respectively. SO stretching bands are found at
c m ‘ 1 which
sulfuric acid
is comparable to
(1 1 8 0
and
1080
those
found
c m ‘ l ) 3 4 2 , 3 4 3
in
the
stretching band appears at a lower frequency.
in
the
proton
NMR
spectrum,
no
1135
and
reported
1025
metallo
These values are another
indication of SO3 H because in the reported SO2 H
However,
difference
ppm which is smaller than that observed
9
in the oxygen bound complexes ( ca.
comparable
betw een
c o m p le x e s ,341
(1 0 0 0
peak
and
7 5 0
assignable
s
O
cm"*)
to
OH
255
resonance is detected, but one of the broad peaks at 7.6 and 3.4 ppm
might be assignable to this resonance because this peak appears at 6.67
ppm in the Cp*Ru(CO)2 (SC>3H) and at 3.89 ppm in Cp*Mo(CO)3S 0 2 H. A
reaction using RuD(NO)(Cyttp) did. not provide much information. OH
stretching
frequencies
hardly
shifted
and
deuterium
NMR
spectrum
cannot pinpoint the resonance of OH. Little shift by introduction of
isotopes is also observed in the SO2 H and SO3 H complexes. Even though
the OH resonance peak cannot
be assigned, other spectroscopic
analytical data support the formulation of this complex
and
as a mctallo
sulfuric acid. On the basis of 3 1 p NMR spectrum, TBP with linear NO is
assigned to this complex.( Equation
107 )
l ^ 'R u —
SO 3 H
(107)
e.
O thers
Reactions
with
CO2 and carbodiimides did not proceed at all. For the
carbodiimide cases,
because
factors
may
be
a reason
for no
reaction
[RuH2 (N O )(C y ttp )]B F 4 does not react with PPI13 while it reacts
with PMe3
W ith
steric
to produce [Ru(PMe3)(N O )(Cyttp)]BF4 .
R uH (N O )(etp)
256
Reactions with CS2 and SO2 produce the same product, etp oxide. These
reactions proceed very fast, and
the reason why etp oxide is the only
product containing phosphorus group is not clear at this point.
i
T"
21
T"
20
I19
“T”
10
~r
17
T
16
T15
~r
14
PPM
T“
13
“T"
~T~
~r
12
11
10
T
9
T
e
257
Fig. 99. 31p{lH } NMR S pectrum of [R u (S 0 3H )(N O )(C yttp)] in CD2C12 a t 101.252 MHz
T
7
INTE6RAL
[
8.5
8 .0
7 .5
6 .5
6 .0
5 .5
PPM
5 .0
4 .5
4 .0
3 .5
3 .0
2 .5
2 .0
258
Fig. 100. !H NMR Spectrum of [R u (S 0 3H)(NO)(Cyttp.)] in CD 2 C I 2 a t 250.133 MHz
0.0
r
A50C
~T~
JOOO
1500
~ r~
IOCO
-500
cm"
* measured as % transmission.
F ig.101. IR S p e c tra o f [R u (S 0 3H ) ( N 0 ) ( C y ttp ) ]
[ R u ( S 0 3D )(N 0 )(C y ttp )] in N u jo l M ull
and
I
T ab le
23.
S pectroscopic
D a ta
of R u(allene-H )(N O )(C yttp)
31p NMR
A lle n e
S o lv e n t
8(CH)
v(NO)
O th e rc
CP 2Q 2
12.04(s)
1630
9 9 5 ,9 8 0
4 4 .4
9.29(s)
1550
1 6 0 0 .1 4 9 0 ,1 4 2 0
15.75
28.3
9.68(s)
1620
1505
16.36
20.8
B enzene
17.18
4 6 .2
CD2C12
1630
v(OH);2450,
2J p p
§P c e n te r
SP w ine
CS2a
14.67
17.62
4 0 .2
PhNCO
2 8 .3 0
8.33
PhNCS
17.15
CH3PhNC5 17.34
9 .5 0
IR b
*H NMR
v(SO); 1135,1025
a. S(CH);246.12(d) 3jpc;10.4Hz in CD2C12
b. IR
spectra is taken in Nujol Mull.
c. v(CX2) are shown
^Chemical shifts, coupling constants and IR stretching frequencies are measured in units of ppm, Hz
and cm-1.
260
C h a p te r V. CONCLUSIONS
1.
The
S tructure
triphosphines.
geometry
is
2.
RuH (N O )P3 depends
G enerally,
6-m em ber
on
chelating
the
nature
ligands
of
favor
chelating
m eridional
and 5-member chelating ligands favor facial geometry. Fluxionality
stopped
undergoes
of
by
introducing
intram olecular
Ruthenium
the
chelating
exchange
dihydridonitrosyl
triphosphines
but fac-RuH(NO)(ttp)
reactions.
complexes
behave
like
m olecular
hydrogen
complexes. Molecular hydrogen is easily replaced by several neutral ligands.
3 . R u H ( N O ) P 3 reduces various unsaturatcd small molecules; usually the Cyttp
complex is more reactive than the etp analogue.
4.
The
type
of
products
acetylenes
depends
acetylenes
react
undergo
insertion
to
on
of
the
the nature
produce
reactions
o f the
acetylide
between
acetylenes.
complexes
while
RuH(NO)(Cyttp)
Nonactivated
activated
and
terminal
acetylenes
reactions.
5. Several oxidants easily oxidize RuH(NO)(Cyttp). Combination of this property
with the great lability of dihydride ligands provides an easy synthetic route to
several unique complexes such as nitrosyl alkoxides.
6. In the 5-coordinate complexes, RuX(NO)(Cyttp), square pyramidal structure
with a bent nitrosyl ligand is favored when X is a
strong electronegative
element such as oxygen and chlorine, while TBP is favored in other cases.
7. Mutual exchange of donor abilities between two flexible ligands present in
the same coordination sphere is not commonly observed probably
high activation barriers to bend the nitrosyl ligand.
261
owing to
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