Phosphane
and
Phosphite
Silver(I)
Complexes:
Synthesis, Reaction Chemistry and their Use as CVD
Precursors
von der Fakultät für Naturwissenschaften der Technische
Universität Chemnitz
genehmigte Dissertation Zur Erlangung des akademischen Grades
doctor rerum naturalium
(Dr. rer. nat.)
Vorgelegt von M.Sc. Patrice DJIELE NGAMENI
Geboren am 29.04.1973 in Fondjomekwet, Kamerun
Eingereicht am 09.11.2004
Gutachter: Prof. Dr. Heinrich Lang
Prof. Dr. Stefan Spange
Prof. Dr. Katharina Kohse-Höinghaus
Tag der Verteidigung: 27.01.2005
http://archiv.tu-chemnitz.de/pub/2005/0008
Bibliographische Beschreibung und Referat
Bibliographische Beschreibung und Referat
DJIELE NGAMENI, Patrice
Phosphane
and
Phosphite
Silver(I)
Complexes:
Synthesis, Reaction Chemistry and their Use as CVD
Precursors
Technische Universität Chemnitz, Fakultät für
Naturwissenschaften
Dissertation, 2004, 144 Seiten
Silber(I)
Komplexe
LnAgX
(X
=
organische
Ligand,
Z.
B.
Carboxylate, Dicarboxylate, Schiff Base; L = Lewis-Base, Z. B.
PnBu3, P(OMe)3, P(OEt)3; n = 1, 2, 3) wurden Bezug auf ihre
Eignung
für
Silberfilmen
die
chemische
synthetisiert
und
Gasphasenabscheidung
charakterisiert.
Von
von
einigen
dieser Verbindung konnten Einkristalle erhalten werden. Der
Bau
dieser
Verbindungen
Röntgeneinkristallographie
wurde
ermittelt.
mittels
Ausgewählten
Verbindungen wurden mit Temperatur-programmierter und in-situ
Massenspektrometrie
mechanismen
für
analysiert.
einige
Abscheidungsexperimente
Gasphasenabscheidungs-
Prekursoren
wurden
sind
vorgestellt.
entsprechend
den
CVD-
Ergebnissen
der Gasphaseanalyse durchgeführt. Silber Schichten konnten mit
einen
Kaltwand
CVD-Reaktor
erzeugt
werden,
deren
Oberflächenmorphologie wurde untersucht.
Stichworte:
Silber,
Dicarboxylate,
röntgensstrukturen,
Silber(I)-Carboxylate,
Schiff-Base,
Chemische
Synthese,
Disilber(I)Einkristall-
Gasphasenabscheidung,
Massenspektrometrie, Oberflächen-Analytik.
Abstract
Phosphane
and
Phosphite
Silver(I)
Complexes:
Synthesis, Reaction Chemistry and their Use as CVD
Precursors
by
M. Sc. DJIELE NGAMENI, Patrice
Chairman: Prof. Dr. LANG, Heinrich
Abstract
Silver(I) complexes of type LnAgX (X = organic ligand,
such as carboxylates, dicarboxylates, Schiff-base; L = Lewisbases, e. g. PnBu3, P(OMe)3, P(OEt)3; n = 1, 2, 3) have been
synthesized
and
characterized
with
respect
to
their
suitability for the Chemical Vapour Deposition (CVD) of silver
thin films. For some of these compounds single crystal could
be
obtained.
single
Their
crystal
solid-state
X-ray
structure
diffraction.
The
was
determined
volatility,
by
thermal
stability, and gas phase decomposition mechanism of selected
compounds were studied using temperature-programmed and insitu
mass
spectrometry.
CVD
experiments
were
performed
according to the results of the gas phase analysis. Silver
films could be grown by using a cold-wall CVD reactor. The
morphology of the latter films was determined.
Keywords:
Silver,
Silver(I)-Carboxylates,
Bisilver(I)-
Dicarboxylates, Schiff-base, Synthesis, Solid-state structure,
Chemical
Vapour
Deposition studies.
Deposition
(CVD),
Mass
spectrometry,
Dedication
To
my parents and my grandmother
1
Table of Contents
Abbreviations
3
1
Introduction
5
2
State-of-Knowledge
8
3
Synthesis of Phosphane- and Phosphite-stabilized
silver(I) complexes of type: [(nBu3P)mAgX],
[{(OR)3P}mAgX], [(nBu3P)mAgEAg(PnBu3)m] (m = 1, 2, 3; R =
Me, Et; X = Carboxylate, E = Dicarboxylate)
11
3.1
Synthesis
of
Silver(I)-Carboxylates
Dicarboxylates [AgEAg]
3.1.1
Spectroscopic studies
Dicarboxylates
3.2
Synthesis of Silver(I)-Carboxylates of type [(nBu3P)AgX] and 16
[{(OR)3P}AgX] (R = Me, Et)
3.2.1
Spectroscopic
complexes
studies
of
[(nBu3P)AgX]
and
[{(OR)3P}AgX] 18
3.2.2
TG and DSC
complexes
studies
of
[(nBu3P)AgX]
and
[{(OR)3P}AgX] 21
3.3
Synthesis of Silver(I)-Carboxylates of type [(nBu3P)2AgX] and 26
[{(OR)3P}2AgX] (R = Me, Et)
3.3.1
Spectroscopic
complexes
3.3.2
Solid-state Structure of 11C
3.3.3
TG and DSC
complexes
3.4
Synthesis of Silver(I)-Carboxylates of type [(nBu3P)3AgX] and 37
[{(OR)3P}3AgX] (R = Me, Et)
3.4.1
Spectroscopic
complexes
3.4.2
TG and DSC
complexes
3.5
Synthesis of Silver(I) Dicarboxylates [(nBu3P)mAgEAg(PnBu3)m] 42
(m = 1,2,3)
3.5.1
Spectroscopic studies of [(nBu3P)mAgEAg(PnBu3)m] complexes
studies
studies
studies
studies
of
Silver(I)-Carboxylates
[(nBu3P)2AgX]
of
of
[AgX]
and
and
and
- 12
- 14
[{(OR)3P}2AgX] 27
30
[(nBu3P)2AgX]
and
[{(OR)3P}2AgX] 33
of
[(nBu3P)3AgX]
and
[{(OR)3P}3AgX] 38
of
[(nBu3P)3AgX]
and
[{(OR)3P}3AgX] 40
43
Table of Contents
2
3.5.2
TG and DSC studies of [(nBu3P)mAgEAg(PnBu3)m] complexes
4
Synthesis of Silver Schiff-base complexes of type: 47
[(nBu3P)mAg{O-2-(C6H4)C(H)N(C6H4)-4-R}] (R = OMe, Me; m =
1, 2)
4.1
Synthesis of Silver(I) Schiff-base Complexes
47
4.1.1
Spectroscopic studies
48
4.2
Synthesis of the nBu3P Silver(I) Schiff-base of type
[(nBu3P)mAg{O-2-(C6H4)C(H)N(C6H4)-4-R}]
50
4.2.1
Spectroscopic studies
50
4.2.2
Solid-state structure of 21a and 21b
52
4.2.3
TD and DSC studies
55
5
Mass Spectrometric Investigations
58
5.1
Temperature-programmed Mass Spectrometry
58
5.2
In-situ Time-of-Flight Mass Spectrometry
64
6
CVD Experiments
67
6.1
Device Description
67
6.2
Film Characterization
69
7
Experimental Section
72
7.1
Instruments and Measurements Conditions
72
7.2
Starting Materials
76
7.3
Synthesis Procedure and Experimental Data
77
7.4
Crystal Refinement Data
124
8
Summary
127
9
References
131
Personal Data
139
Acknowledgement
142
Selbständigkeitserklärung
144
45
Abbreviations
Abbreviations
Å
CVD
n
Bu
Et
Me
DMSO
DMF
Et2O
THF
min
Mp
Angström
Chemical Vapour Deposition
n-Butyl, nC4H9
Ethyl, CH3CH2
Methyl, CH3
Dimethylsulfoxide, (CH3)2SO
Dimethylformamide, HCON(CH3)2
NEt3
Ph
mL
Triethylamine, N(C2H5)3
Phenyl, C6H5
Milliliter
L
sccm
eV
K
kv
Lewis-base
Standard cubic centimeter, cm-3
Electron Volt
Kelvin
Kilo Volt
C
ms
mm
nm
XRD
SEM
J
g
Eq
TG
Tbegin
Tend
∆m
DSC
Celsius
Millisecond
Millimeter
Nanometer
X-Ray Diffraction
Scanning Electron Microscopy
Joule
Gramm
Equation
Thermogravimetry
Temperature at the beginning of measurement
Temperature at the end of measurement
Weight loss (%)
Differential Scanning Calorimetry
∆H
Ca.
Enthalpy (J/g)
About
e. g.
For example
Compd.
compound
Temp.
Temperature
Tevap
Temperature of evaporation
Diethyl ether
Tetrahydrofuran
Minute
Melting point
3
Abbreviations
IR
Infrared
ν
cm-1
w
m
s
vs
Stretching frequency
Wave number
Weak
Medium
Sharp
Very Sharp
NMR
Nuclear Magnetic Resonance
δ
s
bs
d
m
t
q
Chemical shift
Singlet
Broad signal
Dublet
Multiplet
Triplet
Quartet
4
5
Theoretical Section
1 Introduction
Silver has many properties that make it a very useful and
precious metal. Of all metals, silver exhibits, for example,
the lowest resistivity and the highest thermal conductivity at
room
temperature
studied
Scale
as
[1].
potential
Integration
applications
For
interconnect
(ULSI)
in
these
reasons
silver
material
technology.
It
for
also
has
Ultra
has
optoelectronic-mechanical
been
Large
potential
systems
and
reflexive mirror arrays [2-6].
Several processes such as sputtering [7], electron beam
evaporation
[8],
molecular
beam
epitaxy
[9],
photochemical
deposition [10] and Chemical Vapour Deposition (CVD) [11] have
been investigated for the growth of silver thin films. CVD has
a
number
of
key
advantages
in
depositing
metal
films;
it
allows the performance of coatings on large surface areas,
high film uniformity, good deposition control, high deposition
rates
and
excellent
conformal
step
coverage
on
device
structures with dimension below 2 µm, which are important in
microelectronic applications [11,12].
The production of a desired thin film material via CVD
requires an integrated approach involving the selection of the
precursor
and
the
deposition
technique.
The
general
characteristics of an ideal precursor can be summarized as
follows:
-Volatility: the precursor should have a good volatility and
thermal stability during its evaporation and transportation in
the gas phase.
-Purity and reactivity: the precursor should be of high purity
and
decompose
cleanly
on
pyrolysis
without
decomposition
byproducts.
-Stability:
the
precursor
should
be
stable
in
its
storage
container over a long period of time (ca. 6 months).
-Cost: the precursor should be available in consistent quality
and quantity at low cost [2,13].
6
Theoretical Section
A
good
particularly
understanding
for
of
tungsten,
CVD
exists
aluminium
and
for
some
copper
metals,
[2].
For
example a large number of Cu(I) precursors of general formula
LnCu(I)X (X = alkyl, alkoxy, β-diketonate, β-ketoiminate, …; L
= Lewis-base, phosphine, olefin, alkyne; n = 1, 2, 3) are well
known [14,15]. (Vtms)Cu(hfac) (Cupra SelectTM) [16-18] is the
Commercial available Cu(I) precursor.
It is anticipated that there will be a need to change the
interconnect
ultrafast
respect,
lower
material
materials
silver
aluminium
≈
in
is
resistance
2.7
from
aluminium
or
microelectronic
an
excellent
(copper
≈
µΩcm)
circuitry.
choice,
µΩcm,
1.7
[2]
and
tungsten
since
good
In
it
≈
silver
to
new
this
exhibits
µΩcm,
1.6
electromigration
performance [19-21]. On the other hand, silver complexes are
inexpensive
and
provide
economical
alternative
to
more
expensive metal precursors. However, there have only been few
investigations into silver CVD. A great deal of research is
still
necessary,
because
up
to
now
there
is
no
general
agreement on the deposition method, the precursor choice and
the gas phase decomposition mechanism in silver CVD.
The purpose of this study was to synthesize new organosilver(I) complexes and to test them as suitable precursor in
silver CVD. Potential organic ligand which have been used are
carboxylates, dicarboxylates and Schiff-bases. As lewis-base
PnBu3, P(OMe)3, and P(OEt)3 were applied.
In Section 3, the synthesis of phosphane and phosphite
stabilized silver(I) complexes of type (nBu3P)mAgX, [P(OR)3]mAgX
and
(nBu3P)mAgEAg(PnBu3)m
carboxylates;
E
=
(m
=
1,2,3;
dicarboxylates)
R
is
=
Me,
Et;
discussed.
X
=
The
preparation of the phosphane-stabilized silver(I) Schiff-base
complexes [(nBu3P)mAg{O-2-(C4H6)C(H)N(C4H6)-4-R}] (R = OMe, Me;
m = 1, 2) will be discussed in Section 4.
7
Theoretical Section
These
analysis,
complexes
IR,
1
H-,
have
13
been
C{1H}-,
31
characterized
P{1H}-NMR
by
elemental
spectroscopy.
The
thermal behaviour of the respective silver(I) complexes was
investigated using thermogravimetric and differential scanning
calorimetric analysis. The obtained single crystals of some
species have been characterized by X-ray diffraction studies.
The gas phase study of selected complexes was carried out
using temperature-programmed and in-situ time-of-flight mass
spectrometry. The presence of silver-containing fragments was
used to indicate their volatility and several compounds were
regarded
as
potentially
suited
for
CVD
applications.
The
quality and the microstructure of silver thin films deposited
using
a
vertical
cold-wall
reactor
evaporation system is discussed.
with
a
pulsed
spray
8
Theoretical Section
2 State-of-Knowledge
Silver has the symbol Ag for the roman word Argentum; it
is a white metal that crystallizes in a face-centered cubic
structure having a melting point of 962 °C and a boiling point
of
2215
°C
[22].
Silver
is
present
in
silver
complexes
primarily in the oxydation state +I and less frequently in the
oxidation state +II. The oxidation state +1/2, +2/3, +III and
+IV are rarely observed in silver complexes [22]. Like typical
for group-11 metals of the periodic table of the elements also
silver
forms
oligomer
composition
[AgX]n
Deaggregation
of
addition
of
alkenes
[23-30].
or
(X
polymeric
=
these
Cl,
Br,
silver
Lewis-bases,
such
aggregates
I,
salts
as
Low-aggregated
NO,
can
be
phosphanes,
or
of
general
ClO4)
[22].
realized
by
phosphites
or
mononuclear
silver(I)
complexes are suitable as precursors in the metallization of
silver
by
using
the
Chemical
Vapour
Deposition
process,
because they have for example, a low molecular weight and can
be vaporised at low temperature. Several silver(I) complexes
have been used for the deposition of silver films [2].
Most silver(I) salts, like silver(I) acetate and silver(I)
trifluoroacetylacetonate are non-volatile or decompose during
sublimation [2,31]. Special evaporation techniques have been
used to deposit silver films from silver(I) trifluoroacetate,
silver(I) iodide [32] and silver(I) fluoride [33]. Perfluoro1-methylpropenyl silver(I) has been shown to give pure silver
films in good quality at 973 K [31,32], but the compound is
not easy to handle, because of its sensitivity to air and
moisture. Silver carboxylates [RCOOAgPR´3] and [RCOOAg(PR´3)2]
(R = Me,
tested
in
t
Bu, 2,4,6-Me3C6H2, C3H7, C7F15; R´= Me, Ph) have been
an
aerosol-assisted
CVD
process.
However,
silver
films obtained show carbon and fluorine impurities [34]. Thin
silver layers (≤ 100 nm) have been deposited in the temperature
range
of
493
-
623
K
with
the
complex
[C2F5COOAgPMe3]
as
precursor [35]. Silver films with some carbon impurities have
9
Theoretical Section
been grown from [(L)AgPR3] with R = Me, Et, Ph and L = hfac
(1,1,1,5,5,5-hexafluoro-2,4-acetylacetonate),
dimethyl-6,6,7,7,8,8,8-hep
(dipivaloylmethanato)
fod
(2,2-
tafluoro-3,5-octadienato)
[36,37].
The
complex
and
dpm
[(MeCN)Ag(hfac)]
can be used to produce pure silver films at 250 °C in the
presence of hydrogen [38], and from (BTMSE)Ag(hfac) (BTMSE =
trans-bis(trimethylsilyl)ethene)
grown
by
laser-assisted
pure
CVD
silver
[39].
films
Recently,
can
be
high-quality
silver films have been grown from silver pivalate with a flash
evaporation
results
CVD
were
technique
achieved
[40,41].
in
a
Futhermore
hot-wall
excellent
reactor
using
[Ag(COD)hfac] as precursor (COD = 1,5-cyclooctadiene) [42].
The silver(I) carboxylates [(R´3P)nAgO2CR] (n = 1, 2; R = CF3,
C2F5; R´=
silver
n
Bu3, 2-C6H4CH2NMe2) were tested for the deposition of
on
TiN-coated
oxidized
silicon
wafer
by
the
CVD
process. Dense silver layers were formed with silver particle
sizes between 50 and 100 nm [43]. Smooth and high reflective
silver
films
were
deposited
from
silver
carboxylates
by
aerosol-assisted CVD [44]. A Similar deposition technique was
used
to
deposit
silver
from
the
silver
aryloxide-
triphenylphosphine complexes [Ag(OR)(PPh3)] (R = C6H2-2,4,6-Cl3,
C6H4-2-Me, C6H2-2,4,6-(CH2NMe2)3) and {[Ag(OR)(PPh3)3]:ROH} (R =
Ph, C6H4-2-Me) [45], although the quality of the film was poor.
The
majority
of
these
known
silver(I)
CVD
precursors
exhibit, however, a low stability in the gas phase, and hence
insufficcient information is available about the behaviour in
the gas phase upon evaporation and during deposition.
A
free
radical
mechanism
was
proposed
in
the
thermal
decomposition study of neophyl(tri-n-butylphosphine) silver(I)
[46].
Thermal
decomposition
of
silver(I)
complexes
with
triphenylphosphine and aliphatic carboxylates studied between
293 - 973 K in nitrogen as inert gas, showed a multistage
decomposition
where
between
-
605
683
metallic
K
silver
[47].
It
formation
was
was
reported
observed
that
the
decomposition of silver(I) carboxylates proceed in two steps
10
Theoretical Section
[48].
Firstly
the
decarboxylation
occurs
and
secondly
the
formation of metallic silver with the recombination of free
radicals takes place (equation 1).
CO2
[AgO2CR]
T
[AgR]
T
Ag0
+
1/2 R2 +
(1)
X
X = byproducts
Also
the
methylpropenyl
decomposition
silver(I)
was
decomposition products using
mechanism
investigated
13
C and
19
of
by
perfluoro-1analysing
the
F NMR spectroscopy. The
following decomposition mechanism was proposed (equations 2
and 3) [49].
CF3
CF3
[AgF] +
F
F3CC
CCF3
(2)
Ag
Ag0
[AgF]
+
(3)
1/2 F2
For [C2F5CO2Ag], [C2F5CO2AgPMe3] and [(CH3)3CCO2Ag] the gas
phase
decomposition
upon
evaporation
has
been
investigated
using IR, NMR and MS techniques [35,39]. Recently, the gas
phase behaviour of [RCO2Ag] and [RCO2Ag(PnBu3)2] (R = CF3, C2F5)
was studied under near deposition conditions. These studies
showed that only phosphine silver(I) carboxylates are suitable
as
CVD
precursor
[50].
Further
investigations
of
the
decomposition process of Ag CVD precursors are lacking, as
well as systematic examination of different CVD strategies.
In this work we present the synthesis of new silver(I)
complexes which are suitable silver CVD precursors. The gas
phase study using mass spectrometric investigations and the
deposition of silver by pulsed spray evaporation CVD is also
reported.
11
Theoretical Section
3
Synthesis
of
Silver(I)
Phosphane-
Complexes
and
of
Phosphite-stabilized
[(nBu3P)mAgX],
type
[{(OR)3P}mAgX] and [(nBu3P)mAgEAg(PnBu3)m] (m = 1, 2,
3;
R
=
Me,
Et;
X
=
Carboxylates;
E
=
Dicarboxylates)
Silver(I) complexes play an important role in organic and
organometallic synthesis [51-55]. In this context, silver(I)
carboxylates are of significance for the preparation of alkyl
halides
(Hunsdiecker
reaction)
by
their
degradation
with
halogens or give an easy access to esters (Simonini reaction)
[56-58].
Their
application
powerful
precursor
in
the
in
material
CVD
sciences,
process
has
such
already
as
been
illustrated in Section 2.
For the synthesis of new silver(I) CVD precursors it is
necessary
to
choose
inexpensive
but
efficient
chemicals
to
provide economical aspects. These Lewis-bases PnBu3, P(OMe)3
and P(OEt)3) satisfy this criteria and most silver(I) complexes
stabilized
by
these
ligand
are
in
liquid
form.
They
are
therefore potentially suited as CVD precursors in the silver
deposition process.
Phosphane-
and
phosphite-
stabilized
organo-silver(I)
complexes of type XAgR (X = 2-electron Lewis-base, R = organic
group)
can
be
prepared
by
the
following
strategies:
the
reaction of [XAgNO3] with CH-acidic substrates, or treatment of
[AgNO3] with R- and then with X [36,59]. It appeared that the
latter method is the most favoured one in terms of yield and
synthesis conditions. Out of these reasons this strategy was
used in the synthesis of the title complexes. The reactions
should be carried out in the dark to avoid the decomposition
upon formation of elemental silver during the course of the
reaction.
These silver(I) complexes were prepared in different molar
ratios (m = 1, 2, 3) in order to get more stable complexes.
12
Theoretical Section
3.1
Synthesis
of
Silver(I)-carboxylates
[AgX]
and
[AgEAg]
are
-Dicarboxylates [AgEAg]
The
necessary
accessible
by
silver
reacting
salts
[AgNO3]
[AgX]
and
with
the
corresponding
carboxylic (HX) or dicarboxylic acid (H2E) in the presence of
NEt3 in ethanol/acetonitrile mixture (6 : 1). After appropriate
work-up,
the
silver(I)
salts
can
be
isolated
as
light-
sensitive solids in good yield.
HX
+
1a−1j
H2E
[AgNO3]
2
+
1k−1m
2 [AgNO3]
2
NEt3
-HNEt3+NO3-
2NEt3
-2HNEt3+NO3-
[AgX]
(4)
3a−3j
[AgEAg]
(5)
3k−3m
The silver salts obtained are white solids; except 3h
which is brown.
These complexes are poorly soluble in most common polar
organic
solvents,
dimethylformamide
such
(DMF).
as
Due
dimethylsulfoxide
to
this
low
(DMSO)
solubility,
or
which
favour multinuclear structures, complexes 3d - 3m could only
be characterized by IR spectroscopy and elemental analysis.
Structures of X or E of 3a – 3m are recapitulated in Table
1.
13
Theoretical Section
Table 1: Structures of X or E in 3a – 3m.
Compd.
X
Compd.
CH3
3a
H3C
C
3h
C
O
CH3
HO
O
O
CH3
3b
X/E
C
O
O
C
3i
C
H3C
O
C
C
O
O
CH3
O
O
O
CH2
3c
C
O
O
3d
CH C
O
3j
CH3CH2
O
C
H3C
O
O
O
O
O
O
CH3
CH3(CH2)10
C
3m
O
O
3g
O
C CH2CH2 C
3l
O
3f
CH2 C
O
C
C
O
O
C
O
H
C
O
3k
O
3e
C
O
O
C
O
O
C
S
C
O
14
Theoretical Section
3.1.1
Spectroscopic
studies
of
Silver(I)-Carboxylates
and
-Dicarboxylates
IR Spectroscopy
Infrared spectroscopy can help to determine the mode of
coordination of carboxylic groups to the silver atom in the
silver carboxylates [AgX] and silver dicarboxylates [AgEAg].
The carboxylate can act as monodentate (A) , bidentate
(chelate)
( B)
or
bridging(C)
ligand
in
transition
metal
chemistry [60-62].
O
O
C
M
R
M
C
M
R
C
O
O
A
O
M
R
O
C
B
Figure 1: Coordination modes of carboxylic ligands in
transition metal chemistry. [60-62]
A
relationship
between
the
mode
of
coordination
of
carboxylic ligands to metals and the carbon-oxygen stretching
frequency was established [62]. The value ∆ν equals to the
difference
between
the
antisymmetric
stretching
frequency
(νCO2,as) and the symmetric stretching frequency (νCO2,s) of the
free acetate ion (∆ν = 164 cm-1) was considered to be the limit
between
monodentate,
bidentate
and
bridging
modes
of
coordination [62]. For a η1-coordination (monodentate), which
means that the metal is bounded to one oxygen atom, ∆ν of the
complex is much larger (∆ν > 200 cm-1) than the value of the
free acetate ion. In a η2-coordination (bidentate) mode, where
the metal is bound to two oxygen atoms, ∆ν is significantly
smaller (∆ν < 100 cm-1) than the value of the free acetate ion.
∆ν value of complexes which possess a bridging carboxylic unit
15
Theoretical Section
are close to the value of the free acetate ion (∆ν = 164 cm-1)
[62].
∆ν
values
of
complexes
3a
-
and
3m
the
correponding
coordination mode are presented in table 2.
Table 2: Coordination modes of X or E in complexes 3a - 3m.
Compd.
∆ν(cm-1)
Coordination
Compd.
∆ν(cm-1)
Coordination
mode
modes
3a
132
Bridging (C)
3h
166
Bridging (C)
3b
155
Bridging (C)
3i
240
Monodentate(A)
3c
185
Bridging (C)
3j
250
Monodentate(A)
3d
233
Monodentate(A)
3k
165
Bridging (C)
3e
185
Bridging (C)
3l
172
Bridging (C)
3f
142
Bridging (C)
3m
187
Bridging (C)
3g
202
Monodentate(A)
to
the
∆ν
found
for
the
According
modes
were
values
obtained,
silver(I)
two
coordination
carboxylates
3a
–
3j.
However complexes 3k, 3l and 3m give only a bridging mode of
coordination. Also complexes 3a, 3b, 3c, 3e, 3f and 3h exhibit
a bridging mode of coordination (∆ν value are close to 164 cm1
).
Whereas
in
complexes
3d,
3i
and
3j
a
monodentate
coordination mode are typical.
Despite of the poor solubility of the silver(I) complexes
3a - 3m in organic solvents, compounds 3a, 3b and 3c have been
characterized by NMR spectroscopy.
NMR Spectroscopy
The
1
H and
13
C{1H} NMR spectra of 3a and 3b were measured
in d6-DMSO. Due to the low solubility of complex 3c, only the
1
H NMR spectrum could be measured in this solvent.
16
Theoretical Section
The
1
H NMR spectrum of 3a consist of a singlet at 1.08 ppm
for the methyl protons. For 3b a singlet is found at 1.22 ppm
and
can
be
assigned
to
the
methyl
hydrogen
atoms;
the
resonance signal for the OH group is observed at 4.31 ppm. For
3c a singlet is found at 3.44 ppm which can be assigned to the
methylene group, whereas the phenyl group appears as multiplet
in the range of 7.19 - 7.25 ppm.
The
13
C{1H} NMR spectrum of 3a shows three signals at 16.4
(CH3), 29.7 [(CH3)3C], 182.7 (CO) ppm. For 3b following signals
are typical: 29.46 (CH3), 73.03 (HOC), 181.44 (CO) ppm.
Chemical shifts found in the
1
H and
13
C{1H} NMR spectra of
these compounds are characteristic [63,64].
Complexes
[AgX]
and
[AgEAg]
(3a
-
3m)
are
starting
material for the synthesis of the corresponding phosphane and
phosphite
silver(I)
complexes
(PnBu3)mAgX,
[P(OR)3]mAgX,
and
(nBu3P)mAgEAg(PnBu3)m (see below).
3.2 Synthesis of Silver(I)-Carboxylates of type [(nBu3P)AgX]
and [{(OR)3P}AgX] (R = Me, Et)
Monophosphane-
and
monophosphite-stabilized
silver(I)
carboxylates were successfully synthesized by the addition of
PnBu3 (4), P(OMe)3 (5) or P(OEt)3 (6) to a suspension of the
silver salts 3a - 3j in diethyl ether or tetrahydrofuran at 25
°C (equations 6, 7 and 8).
[AgX]
+
3a,3c−3g,
3i,3j
PnBu3
4
[AgX]
+
3a, 3b, 3g
P(OMe)3
5
[AgX]
3a, 3b
+
P(OEt)3
6
Et2O or THF
25 °C
Et2O or THF
25 °C
Et2O
25 °C
[(nBu3P)AgX]
7a−7h
(6)
[{(MeO)3P}AgX]
8a, 8b, 8c
(7)
[{(OEt)3P}AgX]
(8)
9a, 9b
17
Theoretical Section
The synthesis of 8a, 8b, 9a and 9b can be performed in
diethyl ether. Due to the very poor solubility of complexes 3c
- 3j in organic solvents, complexes 7a – 7h and 8c must be
synthesised
in
tetrahydrofuran.
observed,
when
dissolved.
The
a
much
Generally,
the
more
the
respective
obtained
polar
end
silver
reaction
solvent
of
the
salts
mixtures
reaction
are
are
such
as
is
completely
purified
by
filtration through a pad of celite. For complexes 7f, 8a and
8c the suspension persisted during the reaction accompanied by
a change of color. In this case the solvent was removed in
oil-pump vacuum and the complexes were isolated as solids with
melting points of 45 - 70 °C. Complexes 7a - 7e, 7g, 7h, 8b,
9a and 9b are liquids.
Silver(I) complexes 7 – 9 are light, air sensitive and
stable at room temperature for a five days. They were stored
at –30 °C to avoid possible decomposition.
The building blocks of X in 7a - 7h, 8a - 8c, 9a and 9b
are summarized in Table 3.
18
Theoretical Section
Table 3: Structrures of X in 7a - 7h, 8a - 8c, 9a and 9b.
Compound
X
Compound
CH3
7a
8a
H3C
C
9a
X
O
7f
O
O
8c
C
C
O
O
CH3
O
CH2
7b
C
O
7g
O
H3C
O
C
C
O
O
O
7c
7h
CH C
CH3CH2
O
C
C
O
O
O
H
7d
C
C
H3C
9b
O
C
CH3
8b
HO
C
CH3
CH3
O
C
O
O
CH3(CH2)10
7e
C
O
3.2.1 Spectroscopic studies of [(nBu3P)AgX] and [{(OR)3P}AgX]
complexes
IR Spectroscopy
In
the
monophosphane
and
monophosphite
silver(I)
carboxylate complexes 7 – 9, the difference between asymmetric
and symmetric carbon-oxygen stretching frequencies allow to
determine the coordination mode of the carboxylic units. ∆ν
values of the corresponding silver(I) complexes are given in
Table 4.
19
Theoretical Section
Table 4: Coordination modes of X in 7a - 7h, 8a, 8b, 8c, 9a
and 9b.
Compd.
∆ν(cm-1)
Coordination
7a
7b
133
183
mode
Bridging (C)
Bridging (C)
7c
7d
7e
7f
208
166
172
196
Monodentate(A)
Bridging (C)
Bridging (C)
Bridging (C)
7g
209
Monodentate(A)
Compd.
∆ν(cm-1)
Coordination
7h
8a
233
155
mode
Monodentate(A)
Bridging (C)
8b
8c
9a
9b
172
203
141
190
Bridging (C)
Monodentate(A)
Bridging (C)
Bridging (C)
Two modes of coordination (monodentate or bridging) of the
carboxylic units are found. A bridging coordination mode is
typical for 7a, 7b, 7d, 7e, 7f, 8a, 8b, 9a and 9b. However, in
complexes 7c, 7g, 7h, and 8c a monodentate coordination mode
is characteristic.
Complexes 7 - 9 are soluble in deuterated chloroform.
Therefore, these compounds were characterized by
31
1
H,
13
C{1H} and
P{1H} NMR spectroscopy.
NMR Spectroscopy
According to signal integration a 1:1 ratio of AgX to
phosphane or phosphite ligands could be proved in the
1
For the Phosphane silver(I) carboxyltates 7a – 7h in the
spectra triplets at 0.73 - 0.90 ppm with
and
multiplets
at
0.88
-
1.65
ppm
are
3
H NMR.
1
H-NMR
JHH = 5.0 - 7.10 Hz
found
and
can
be
assigned to the CH3 and CH2 entities of the PnBu3 ligand. For
the respective phosphite silver(I) complexes [{(OMe)P}3AgX], a
doublet at ca. 3.5 ppm with
protons are observed in the
2
1
JPH = 13.5 Hz for the methoxy
H NMR spectra. Furthermore the
triethylphosphite species of [{(OEt)3P}AgX] show a triplet at
1.09 ppm (9a) and 1.34 ppm (9b) with
3
JHH = 7.11 and 7.50 Hz
respectively and can be assigned to CH3 hydrogen atoms. For the
CH2 units a multiplet is observed between 3.77 - 4.17 ppm.
20
Theoretical Section
The chemical shifts and the coupling constants of the
phosphane and phosphite entities in 7a – 7h , 8a – 8c, 9a, 9b
are
close
to
the
value
of
the
free
ligand
[63-65].
Also
signals for the carboxylate groups X could be detected. Their
chemical shifts and coupling constants are also in the range
of respective carboxylates [63-65]. However, coordination of
the phosphane or phosphite ligands to silver could not be
proofed by 1H NMR studies.
13
C{1H} NMR spectra contain well-resolved signals for each
organic group. The CH2 entities of the PnBu3 ligand resonate as
3
doublets between 24 - 28 ppm with
1
23 Hz and
JPC = 14 - 15 Hz,
2
JPC = 20-
JPC = 3-4 Hz. Their CH3 group appears as singlet at
ca. 13 ppm. The chemical shifts and coupling constants found
are in the range of known values [63-66]. For 8a, 8b and 8c
which contain trimethylphosphite ligand, doublets are found
which can be assigned to OCH3 group (51.7 – 52.2 ppm with
4.40 Hz,
13
2
JPC = 3.6 Hz and
2
2
JPC =
JPC = 4.8 Hz). Similarly, in the
C{1H} NMR spectrum of 9b, the P(OEt)3 ligand gives rise to two
doublets at 16.7 and 61.9 ppm with
3
JPC = 6.8 Hz and
2
JCP = 4.3
Hz.
The coordination of the respective phosphane or phosphite
ligands
to
the
demonstrated by
31
silver(I)
center
in
7
-
9
signals
nicely
P{1H} NMR spectroscopic studies. Through the
dative-binding of the phosphorus atom to silver the
resonance
is
are
shifted
to
a
lower
or
31
P{1H} NMR
higher
field
compared to the non-coordinated phosphane [PnBu3 (-32.3 ppm)]
or phosphites [P(OMe)3, 138.2 ppm; P(OEt)3, 137.6 ppm]. This
finding is in agreement with the observation generally made by
changing from non-coordinated to datively-bound phosphane or
phosphites in silver(I) chemistry [36,55,67].
The
31
P{1H}-NMR Chemical shifts of complexes 7a - 7h, 8a,
8b, 8c, 9a and 9b are summarized in Table 5.
The
31
P{1H} NMR resonances of
n
Bu3P-silver(I) complexes are
shifted to lower field compared to free
n
Bu3P, while the
31
P{1H}
NMR signals of the phosphite silver carboxylates appear at
21
Theoretical Section
higher
field
Generally
compared
the
most
to
the
significant
respective
free
feature
the
in
phosphite.
31
P{1H}
NMR
spectra of the silver complexes is the shift of the resonance
signals.
This
shift
is
however,
greater
for
the
phosphane
species than for the phophites ones. This fact can be assigned
to
the
high
attraction
of
the
electron
shell
in
silver-
phosphorus bonds by phosphane rather than by phosphites.
Table 5: Comparison of the
31
P{1H} NMR chemical shifts of 7a-
7h, 8a, 8b, 8c, 9a and 9b with the respective free
phosphane or phosphites.
Compd.
δ[ppm] Compd.
δ[ppm] Compd.
δ[ppm]
Compd.
δ[ppm]
PnBu3(4)
-32.3
PnBu3(4)
-32.3
7a
-0.4
7e
-1.2
8a
128.9
9a
123.9
7b
0.5
7f
0.3
8b
126.3
9b
121.1
7c
-1.5
7g
-1.1
8c
129.2
7d
0.5
7h
-0.0
Doublets are found in the
1
with
the
31
JAg31P = 903.3 Hz and
3.2.2
P{1H} NMR spectra of 7e and 7f
JAg31P = 715.1 Hz. At low temperature,
P{ H} NMR of 7b shows a distinguished resonance pattern,
688 Hz and
109
31
137.6
1
107
due to its coupling to
%,
1
P(OMe)3(5) 138.2 P(OEt)3(6)
1
Ag and
109
Ag isotopes with
J109Ag31P = 793 Hz (natural abundances:
107
1
J107Ag31P =
Ag = 51.83
Ag = 48.17 % [22]).
TG
and
DSC
studies
of
[(nBu3P)AgX]
and
[{(OR)3P}AgX]
complexes
Thermogravimetry analysis is extensively used as a first
criterion for the investigation of the thermal behaviour of a
compound.
Thus
the
thermal
decomposition
of
silver(I)
complexes involves the formation of elemental silver and the
number of steps found in the thermogram related to the weight
22
Theoretical Section
loss
allow
the
suggestion
of
a
possible
decomposition
mechanism.
Thermogravimetric analysis is a technique in which few
milligrams of the sample is placed in a porcellan schale and
is heated under nitrogen using a temperature program where the
temperatures at the begining and at the end of the measurement
is defined. The result of the analysis is presented as a graph
with the temperature on the X-axis and the weight procent
relative to the mass of the sample on the Y-axis.
Thermograms of 7a, 7c, 7d and 7g were carried out in the
temperature interval of 20 - 800 °C with a heating rate of 8
°C/min. A summary of these studies are presented in Table 6.
Table 6: TG data of 7a, 7c, 7d and 7g.
Compd. steps Tbegin [°C]
Tend [°C]
∆mexp [%]
∆mtheo [%]
7a
1
152
400
72.43
73.77
7c
3
100/202/
202/242/
8.59/31.72/
8.43/32.07/
242
349
39.6
38.7
7d
1
150
422
71.14
73.64
7g
3
100/174/
174/243/
10.31/51.22/
11.07/50.92/
243
402
9.81
10.83
Tbegin = Temperature at the beginning of decomposition.
Tend =
Temperature at the end of decomposition.
∆mexp = Experimental value of weight loss.
∆mtheo = Theoretical value of weight loss.
23
Theoretical Section
The values of ∆mtheo corresponds to the theoretical weight
loss in the complex relative to the formation of elemental
Weight %
silver.
100
80
60
40
20
0
∆ m = 8 0 .0 %
20
220
420
620
Temperature (°C)
Weight %
Figure 2: TG trace of 7c (heating rate, 8 °C/min).
100
80
60
40
20
0
∆ m
20
220
=
7 1 . 1 4
420
%
620
Temperature (°C)
Figure 3: TG trace of 7d (heating rate, 8 °C/min).
The thermogram of 7c shows a decomposition in 3 steps. The
first step occurs between 100 °C and 202 °C with ∆mexp1 = 8.59 %
which corresponds to the loss of CO2. For the second and third
steps in the 202 - 349 °C range, ∆mexp2 = 31.72 % and ∆mexp3 =
39.68
%
accordance
respectively
with
the
were
loss
found;
of
this
(Ph)2CH.
phenomena
and
are
PnBu3 groups.
in
A
decomposition mechanism for 7c could be proposed (see equation
24
Theoretical Section
9). Similarly, 3 steps are found in the thermogram of complex
7g. The weight losses are equal to 10.31, 51.22 and 9.81 % and
can
be
explained
respectively.
A
by
the
possible
loss
of
CO2,
decomposition
PnBu3
CH3C(O).,
and
mechanism
for
7g
is
given in equation 10. Complexes 7a and 7d decompose in one
step process which starts at 100 °C/150 °C, finishes at 400
°C/422
°C
with
∆mexp
equal
to
72.43
and
71.74
%.
It
was
difficult to suggest a decomposition mechanism in these case.
we expect that the decarboxylation and the loss of both, the
PnBu3 and the alkyl group were so close that these steps could
not separately be found in the thermogram. This fact could be
assigned to the high temperature ramp.
The difference between ∆mexp and ∆mtheo corresponds to –
1.34%, 0.69 %, 2.5 % and –1.48 % for 7a, 7c, 7d and 7g. For 7d
this large difference could be assigned to the presence of
carbon
impurities
which
were
not
totally
removed
from
the
porcellan schale.
[Ph2CHCOOAg(PnBu3)]
T
CO2
n
+ [Ph2CHAg(P Bu3)]
T
Ag0
.
+ Ph2CH
2 Ph2CH.
Ph2CH
[CH3C(O)COOAg(PnBu3)]
CHPh2
CO2
n
+ [CH3C(O)Ag(P Bu3)]
T
Ag0
.
n
+ CH3C(O) + P Bu3
CH3(O)C
Scanning
(9)
T
2 CH3C(O).
Differential
n
+ P Bu3
Calorimetry
(10)
C(O)CH3
(DSC)
is
a
thermal
technique in which differences in heat flow into a substance
and
a
reference
are
measured
as
a
function
of
sample
temperature program [68]. In DSC analysis the mass of the
sample and the peak areas obtained in the thermogram allow to
calculate the enthalpy ∆H of the chemical or physical process
25
Theoretical Section
such as melting, vaporisation, sublimation and decomposition
which occur using the pyris program.
The silver(I) complexes 7 – 9 were also characterized by
DSC studies between 20 - 450 °C with a heat rate of 8 °C/min.
As example, Figure 4 presents the DSC trace of complex 8b
Heat (mV)
30
1
20
10
2
0
0
3
100
200
300
400
500
Temperature (°C)
Figure 4: DSC trace of 8b (heating rate, 8 °C/min).
The DSC trace of 8b shows one exothermic peak at 68 °C
which could be ascribed to the elimination of the coordinated
ligand P(OMe)3. Two endothermic peaks at 151 °C and 170 °C
could
be
assigned
to
the
vaporisation
of
8b
follow
decomposition. ∆H values are summarized in Table 7.
Table 7: DSC data of 8b.
Peak
Temp.(°C)
∆H (J/g)
1
68
66.8
2
151
-151.8
3
170
-102.3
by
a
26
Theoretical Section
3.3 Synthesis of silver(I)-carboxylates of type [(nBu3P)2AgX]
and [{(OR)3P}2AgX] (R= Me, Et)
The monophosphane and monophosphite silver(I) carboxylates
7 – 9 are solids or liquids with high viscosity. However, the
complexation of silver atom with two phosphan or phosphite
ligands should induce further deaggregation and the respective
complexes should be liquids with lower viscosity or solids
having lower melting point.
Diphosphan and diphosphite silver(I) carboxylates can be
synthesized in an analogous manner as described in Section
3.2. (equations 11, 12, 13).
[AgX]
3a,3c−3j
+
[AgX]
+
3a, 3b, 3g
[AgX]
3a, 3b
Et2O or THF
2 PnBu3
4
25 °C
Et2O or THF
2 P(OMe)3
5
25 °C
Et2O
2 P(OEt)3
+
25 °C
6
[(nBu3P)2AgX]
10a−10i
(11)
[{(OMe)3P}2AgX]
11a, 11b, 11c
(12)
[{(OEt)3P}2AgX]
(13)
12a, 12b
The molar ratio between the silver salts [AgX] and the
phosphans or phosphites is 1:2, otherwise a mixture of monoand
diphosphane
or
mono-
and
diphosphites
silver(I)
carboxylates is obtained. Complexes 10 - 12 are liquids; only
complex
11c
is
a
brown
solid.
They
are
more
stable
than
complexes 7 - 9. To avoid possible decomposition they were
stored at –30 °C.
The building blocks of X in 10a - 10i, 11a, 11b, 11c, 12a
and 12b are illustrated in Table 8.
27
Theoretical Section
Table 8: Structures of X in 10a - 10i, 11a - 11c, 12a and 12b.
Compd.
X
Compd.
CH3
10a
11a
H3C
C
12a
X
O
10f
O
O
11c
C
C
O
O
CH3
O
O
CH2
10b
C
10g
O
O
10c
C
O
O
10h
CH C
H3C
O
C
H
O
C
C
H3C
10i
O
C
CH3CH2
O
C
C
O
CH3
O
CH3(CH2)10
10e
C
O
O
10d
O
CH3
11b
C
12b
HO
O
C
O
C
O
CH3
3.3.1 Spectroscopic studies of [(nBu3P)2AgX] and [{(OR)3P}2AgX]
complexes
IR Spectroscopy
IR analysis of 10 - 12 allows to manifest the binding mode
of the carboxylic units to the silver atoms. This is referred
to
the
value
∆ν
relative
to
the
separation
between
the
asymmetric and symmetric carbon-oxygen stretching frequencies.
The binding modes for 10 - 12 are given in Table 9.
O
28
Theoretical Section
Table 9: Binding
mode of X in
10a - 10i, 11a - 11c, 12a and
12b.
Compd.
∆ν(cm-1)
X
Compd.
∆ν(cm-1)
X
10a
159
Bridging (C)
10h
183
Bridging (C)
10b
197
Bridging (C)
10i
216
Monodentate(A)
10c
218
Monodentate(A)
11a
78
bidentate(B)
10d
167
Bridging (C)
11b
192
Bridging (C)
10e
175
Bridging (C)
11c
205
Monodentate(A)
10f
209
Monodentate(A)
12a
139
Bridging (C)
10g
184
Bridging (C)
12b
192
Bridging (C)
Three binding modes are found for 10 – 12. A bridging mode
is favoured for 10a, 10b, 10d, 10e, 10g, 10h, 11a, 11b, 12a
and 12b. For 10c, 10f, 10i and 11c, a δ - binding is typical.
The
IR
result
spectroscopic
of
the
X-ray
data
of
study
complex
of
this
11c
agrees
compound
(see
with
the
Section
3.3.2).
NMR Spectroscopy
The intensity of the resonance signals observed in the
1
H-
NMR spectra confirmed a 1:2 ratio of AgX to the phosphane or
phosphite
ligands.
The
chemical
shifts
and
the
coupling
constant of each organic group of 10a - 10i, 11a, 11b, 11c,
12a and 12b are close to those found in the monophosphane and
monophosphite silver(I) carboxylate complexes 7 – 9 [63-65].
In the
13
C{1H} NMR spectra of 10 - 12, chemical shifts and
coupling constants (3JPC,
ethoxy
entities
of
2
the
JPC,
1
JPC) for the butyl, methoxy and
phosphane
and
phosphite
ligands
correspond almost to those values found (Section 3.2.1). The
chemical shifts values for X are similar to those of the free
carboxylic units and they correspond with the values reported
in the literature [63-66].
29
Theoretical Section
The
1
H
13
C{1H}
and
NMR
spectra
of
–
10
12
give
no
information on the coordination of the phosphorous atoms to
silver. However
31
P{1H} NMR spectra are of some interest, since
they indicate the ligand exchange.
The
31
P{1H} NMR resonance of 10 – 12 found between –6.6 - -
8.6 (10) and 129.1 – 134.2 (11 – 12) (Table 10). This could be
ascribed to the fact that the electron shell around silver
atom are attracted by two phosphorus atoms.
Table 10: Comparison of the chemical shifts of the
31
P{1H} NMR
signals of 10a - 10i, 11a, 11b, 11c, 12a and 12b.
Compd.
δ[ppm] Compd. δ[ppm]
PnBu3(4) -32.3
10e
Compd.
δ[ppm]
Compd.
P(OMe)3(5) 138.2
-7.8
δ[ppm]
P(OEt)3(6) 137.6
10a
-8.1
10f
-6.9
11a
134.2
12a
130.6
10b
-8.4
10g
-8.6
11b
133.5
12b
129.1
10c
-8.2
10h
-6.8
11c
133.4
10d
-8.3
10i
-6.6
In the
31
P{1H} NMR spectra of complexes 10a - 10e, 10g,
10h, 11a, 11b, 11c, 12a, and 12b the resonance signals appear
as a broad signal. Whereas for complexes 10f and 10i a broad
doublet was found with coupling constants of
1
JAg31P equal to 245
Hz and 463 Hz. The broad doublet obtained indicates a fast
intermolecular exchange of phophan or phosphite ligands and
carboxylates
in
solution
coupling constants
1
[36,55,67].
J107Ag31P = 635 Hz and
found in low temperature
31
Two
1
doublets
with
J109Ag31P = 732 Hz were
P{1H} NMR of complex 11c (see Figure
5).
For complex 11c, low temperature
that
the
coalescence
point
which
31
P{1H} NMR studies reveal
correspond
to
the
limit
between the fast and the slow ligand exchange in solution is
around
243
K.
Two
doublet
observed
at
173
K
confirm
the
coordination of the phosphite ligand toward the two silver
isotopes
107
Ag and
109
Ag.
30
Theoretical Section
298 K
243 K
203 K
173 K
139
138
137
136
135
134
133
132
Figure 5: Low temperature
131
31
130
129
128
127
126
P{1H} NMR of 11c.
3.3.2 Solid-state Structure of 11c
Single crystals suitable for X-ray structure analysis were
obtained by cooling a
diethyl ether solution containing 11c
to 0 °C.
The molecular structure of (11c) is shown in Figure 6.
31
Theoretical Section
Figure 6: Crystal structure of (11c), showing two symmetric
independent molecules in the asymmetric unit, the
hydrogen
atoms
have
been
omitted
for
clarity
(Probability of thermal ellipsoids: 50%).
Complex 11c crystallises in the triclinic space group P-1
as two centrosymmetric dimers by formation of a planar Ag2O2
four
membered
ring
built-up
by
a
coordination
of
the
negatively charged oxygen atoms of the carboxylato group and
32
Theoretical Section
the two silver atoms. The Ag atoms are distorded tetrahedrally
coordinated by two oxygen atoms of the central Ag2O2 ring and
the two phosphorus atoms of the trimethylphosphite ligands.
Following bond distances were found in the first symmetric
molecule: Ag(1)-O(1) 2.3788 Å; Ag(1)-O(1A) 2.4228 Å; Ag(1)P(1) 2.4277 Å; Ag(1)-P(2) 2.4017 Å. These distances are close
to those in other silver carboxylate complexes [69-71]. The
Ag-P bond lenghts are close to Ag-O bond. This fact proves
that the phosphate ligands are strongly bonded to the silvers.
The
Ag-P
distances
are
significantly
different
from
each
other.
The carboxylato oxygen atoms are in plane bound with the
central Ag2O2 ring of [{P(OMe)3}2AgO2C(C4H3O)]. The deviation of
the oxygen atom to the calculated mean plane of Ag2O2 is 0.104
Å; also the Ag(1)-O(2) distance with 3.02 Å is shorter than
the sum of the van der Waal´s radii of Ag and O (3.20 Å) [72].
The main difference between the two dimers is the angle of the
furan group toward the central Ag2O2 ring. The angle between
Ag(1)-O(1)-Ag(1A)-O(1A)
toward
C(2)-C(3)-C(4)-C(5)-O(3)
is
9.7°, while the angle between Ag(2)-O(10)-Ag(2A)-O(10A) and
C(13)-C(14)-C(15)-C(16)-O(12) is 34.3°. All bond lengths and
angles of these two units are similar beside the standard
deviation.
Selected
bond
distance
of
the
first
unit
are
reported in table 11. It was the first formation of Ag2O2 ring
with Ag atoms which are coordinated by two phosphorus atoms.
33
Theoretical Section
Table 11: Selected Bond Distances and Angles of 11c.
Bond distances [Å]
Bond angles [°]
Ag(1)-O(1)
2.379(2)
O(1)-Ag(1)-P(1)
108.51(5)
Ag(1)-O(1A)
Ag(1)-P(1)
Ag(1)-P(2)
P(1)-O(4)
O(3)-Ag(1)
O(1)-Ag(2)
2.423(2)
2.428(7)
2.402(6)
1.595(2)
3.286(3)
3.092(4)
O(1A)-Ag(1)-P(1)
P(2)-Ag(1)-P(1)
Ag(1)-O(1)-Ag(1A)
O(8)-P(2)-Ag(1)
C(1)-O(1)-Ag(1)
O(9)-P(2)-Ag(1)
108.44(5)
124.20(2)
106.97(6)
116.39(7)
141.28(1)
113.43(7)
a) The estimated standard deviation of the last significant
digits are shown in parentheses.
R
C
1.26
P 108.44
O
124.20
P
Ag
2.37
O
2.42
106.97 Ag
O
O
141.28
P
2.44
2.41
P
1.24 C
R
Figure 7: Schematic view of 11C.
3.3.3 TG and DSC studies of [(nBu3P)2AgX] and [{(OR)3P}2AgX]
complexes
The thermal behaviour of complexes 10b – 10e was first
investigated by thermogravimetric analysis (Figures 8 and 9).
Table 12 show the respected data.
34
Theoretical Section
Table 12: TG data of 10b - 10e.
Compd. Step(s)
Tbegin [°C]
Tend [°C]
∆mexp [%]
∆mtheo [%]
10b
1
101
376
83.81
83.34
10c
2
101/201
201/352
28.49/56.71
29.14/55.90
10d
1
134
379
78.92
82.36
10e
1
124
399
82.96
84.84
Tbegin = Temperature at the beginning of decomposition.
Tend =
Temperature at the end of decomposition.
∆mexp = Experimental value of weight loss.
Weight %
∆mtheo = Theoretical value of weight loss.
100
80
60
40
20
0
∆m
20
220
=
83.81
420
%
620
Temperature (°C)
Figure 8: TG trace of 10b (heating rate, 8 °C/min).
35
Weight %
Theoretical Section
100
80
60
40
20
0
∆ m
20
220
=
420
8 5 . 2 1
%
620
Temperature (°C)
Figure 9: TG trace of 10c (heating rate, 8 °C/min).
A thermal decomposition in 2 steps was found for 10c. The
first step between 101 °C and 201 °C with ∆m = 28.49 % was
assigned to the loss of CO2 and (Ph)2CH.. The second step (201
- 352 °C) expresses the loss of 2 molecules of PnBu3. The
decomposition mechanism for 10c related to that one typical
for 7c (Section 3.2.2). However, for complex 10b and 10d a one
step decomposition is observed (10b: 101 °C/376 °C; 10d: 124
°C/399 °C) with a weight loss of 83.81 % (10a)/82.96 % (10d).
In
this
case
it
is
difficult
to
predict
a
decomposition
mechanism.
The difference ∆m = ∆mexp - ∆mtheo is 0.47 % for 10b, 0.11%
for
10c,
differences
–3.38
are
%
for
10d
negligible
and
and
–1.88
express
%
for
the
10e.
These
quantitative
formation of metallic silver during the decomposition process.
Differential Scanning Calorimetric studies was carried out
for 10 - 12. As example we have below result obtained for 11c
(Figure 10, Table 13).
.
36
Theoretical Section
Heat (mV)
40
3
30
1
20
10
2
4
0
20
120
220
320
420
520
Temperature (°C)
Figure 10: DSC trace of 11c (heating rate, 8 °C/min).
The DSC trace of 11c shows one exothermic peaks at 42 °C
which can be assigned to the loss of the phosphite ligands.
One
endothermic
peak
at
180.6
°C
close
to
the
second
exothermic peak at 180.9 °C must probably be ascribed to the
vaporisation and the decomposition of 11c. The enthalpies ∆H
assigned to each process are presented (Table 13).
Table 13: DSC data of complex 11c.
Peak
Temperature
∆H (J/g)
1
42
10.10
2
180.6
-14.48
3
180.9
11.87
4
209.6
-13.25
37
Theoretical Section
3.4 Synthesis of silver(I)-carboxylates of type [(nBu3P)3AgX]
and [{(OR)3P}3AgX] (R = Me, Et)
Triphosphane
and
triphosphite
silver(I)
carboxylate
complexes were synthesized in order to obtain compounds with
low aggregation and good stability.
These complexes can be synthesized as outlined in Section
3.2 (equations 14 - 16).
[AgX]
3a,3f−3i
+
3 PnBu3
4
[AgX]
3a, 3b
+
3 P(OMe)3
5
[AgX]
3a, 3b
+
3 P(OEt)3
6
Et2O or THF
25 °C
Et2O or THF
25 °C
Et2O
25 °C
[(nBu3P)3AgX]
13a−13f
(14)
[{(OMe)3P}3AgX]
14a, 14b
(15)
[{(OEt)3P}3AgX]
(16)
15a, 15b
The stoichiometry should be respected, otherwise a mixture
of phosphane or phosphite silver(I) carboxylate complexes will
be obtained. All complexes 13 - 15 are liquids and showing a
good stability. They were stored at –30 °C to avoid possible
decomposition.
Structures
of
the
illustrated in Table 14.
building
blocks
X
in
13
–
15
are
38
Theoretical Section
Table 14: Structures of X in 13 – 15.
Compd.
X
Compd.
CH3
13a
14a
H3C
15a
C
X
O
O
13e
C
H3C
C
O
O
CH3(CH2)10
O
C
13f
CH3CH2
O
O
O
13c
C
O
CH3
13b
O
15b
O
C
C
O
CH3
14b
C
O
HO
C
CH3
O
C
O
O
13d
C
O
O
3.4.1 Spectroscopic studies of [(nBu3P)3AgX] and [{(OR)3P}3AgX]
complexes
IR-Spectroscopy
The value ∆ν (∆ν = νasym – νsym) was determined (Table 15).
Only a bridging mode was found for 13 - 15.
Table 15: Coordination modes of X in 13 - 15.
Compd.
∆ν(cm-1)
X
Compd.
∆ν(cm-1)
X
13a
176
Bridging (C)
13f
197
Bridging (C)
13b
184
Bridging (C)
14a
149
Bridging (C)
13c
196
Bridging (C)
14b
181
Bridging (C)
13d
180
Bridging (C)
15a
167
Bridging (C)
13e
197
Bridging (C)
15b
200
Bridging (C)
39
Theoretical Section
NMR spectroscopy
The integration of the respective
the stoichiometry [AgX] to
n
1
H NMR spectra confirms
Bu3P/(RO)3P = 1:3. Chemical shifts
and coupling constants found in
1
H NMR of complexes 13 - 15 are
close to those ones found for the free carboxylic units. The
same goes for the resonances signals and coupling constants
found of the phosphane or phosphite ligands [63-65].
In the
13
C{1H} NMR spectra of complexes 13 - 15 chemical
shifts and coupling constants related to the
carbon of the
phosphane or phosphite ligands were found. Chemical shifts of
the groups X are similar to those of the free carboxylic units
and they are close to the values reported elsewhere [63-66].
31
P{1H} NMR studies reveal that by going from free
n
Bu3P
and (RO)3P (R = Me, Et) to dativ-bond phosphanes and phosphites
the chemical shifts move upfield towards the values of free
phosphane
or
phosphites.
Chemical
shifts
of
13
-
15
are
summarized in Table 16.
Table 16: Comparison of the chemical shifts of the
31
P{1H}-NMR
signals of 13 – 15.
Compd.
δ[ppm] Compd. δ[ppm]
PnBu3(4) -32.3
Compd.
δ[ppm]
Compd.
δ[ppm]
P(OEt)3(6)
137.6
10e
-7.8
P(OMe)3(5)
138.2
13a
-15.4
13d
-14.8
14a
135.3
15a
132.2
13b
-12.9
13e
-11.4
14b
134.3
15b
131.2
13c
-11.5
13f
-11.2
40
Theoretical Section
3.4.2 TG and DSC studies of [(nBu3P)3AgX] and [{(OR)3P}3AgX]
complexes
Thermal analysis was carried out on selected example (13a
– 13c and 13f) to evaluate their decomposition patterns (Table
17, Figures 11 and 12).
Table 17: TG data of 13a - 13c and 13f.
Compd.
step
Tbegin [°C]
Tend [°C]
∆mexp [%]
∆mtheo [%]
13a
1
100
350
85.17
86.78
13b
1
100
399
87.27
88.20
13c
1
102
354
85.55
86.93
13f
1
103
350
85.03
86.77
Tbegin = Temperature at the beginning of decomposition.
Tend =
Temperature at the end of decomposition.
∆mexp = Experimental value of weight loss.
Weight %
∆mtheo = Theoretical value of weight loss.
100
80
60
40
20
0
∆m
20
220
=
85.17
420
%
620
Temperature (°C)
Figure 11: TG trace of 13a (heating rate, 8 °C/min).
41
Weight %
Theoretical Section
100
80
60
40
20
0
∆m
20
220
=
85.55
420
%
620
Temperature (°C)
Figure 12: TG trace of 13c (heating rate, 8 °C/min).
For complexes 13a - 13c and 13f a one step decomposition
process is found
The difference ∆m = ∆mexp - ∆mtheo are –1.61 % for 13a,–0.93
% for 13b, -1.38 % for 13c and –1.74 % for 13f.
Difference Scanning Calorimetry was additionally carried
out on 13 - 15. As example the result obtained for 15a is
illustrated in figure 13.
22
Heat (mV)
20
18
16
14
12
10
20
120
220
320
Temperature (°C)
Figure 13: DSC trace of 15a (heating rate, 8 °C/min).
42
Theoretical Section
Two exothermic peaks at 175 and 186 °C with ∆H = –1.97 J/g
and–4.25 J/g were found for 15a.
It was presumed that the stability of the above discussed
compounds increases with the number of Lewis-bases. This fact
resembles
the
coordinative
saturation
of
silver,
since
18
valence electrons are reached.
3.5
Synthesis
of
Silver(I)-dicarboxylates
of
type
[(nBu3P)mAgEAg(PnBu3)m] (m = 1, 2, 3)
Silver(I)
dicarboxylates
are
of
great
interest
due
to
their thermal stability [73]. Furthermore, the high content of
silver in these compounds could be an advantage for their use
as
precursors
process.
in
Thus,
the
metallisation
their
potential
of
silver
by
applicability
the
for
CVD
the
deposition of silver thin films was investigated as part of
this Ph.D. study.
Such complexes can be synthesized as shown in equation 17.
[AgO2C
E
3k−3m
CO2Ag]
n
+ m´P Bu3
4
E = CH2, CH2CH2, 2,5-C4H2S
m´ = 2, 4, 6
THF
25 °C
(nBu3P)m AgO2C
E
CO2Ag (PnBu3)m
(17)
16a: E = CH2, m = 2
16b: E = CH2, m = 3
16c: E = CH2CH2, m = 2
16d: E = CH2CH2, m= 3
16e: E = 2,5-C4H2S, m = 1
16f: E = 2,5-C4H2S, m= 2
Complexes 16a - 16f were prepared by the addition of PnBu3
to a suspension of silver(I) salts 3k - 3m in tetrahydrofuran
at 25 °C.
For E = CH2, CH2CH2 the reaction was possible only whith m´
= 4 and 6. However for E = 2,5-C4H2S stable compounds could
only be obtained for m´ = 2 and 4. complexes 16 are liquids
except 16f which is a solid with melting point of 42 °C.
43
Theoretical Section
Complexes 16a - 16f are light and air sensitive. They are
generally stable at room temperature, but start to decomposed
after four days. They are best stored at –30 °C.
3.5.1 Spectroscopic studies of [(nBu3P)mAgEAg(PnBu3)m] complexes
IR Spectroscopy
Complexes
–
16a
16f
were
spectroscopy. ∆ν = νasym,CO – νsym,
CO
characterized
by
infrared
were determine (table 18).
Table 18: Binding mode of E in 16a - 16f.
Compd.
∆ν(cm-1)
E
Compd.
∆ν(cm-1)
E
16a
141
Bridging (C)
16d
185
Bridging (C)
16b
136
Bridging (C)
16e
239
Monodentate (A)
16c
172
Bridging (C)
16f
227
Monodentate (A)
Additionally, 16a – 16f were characterized by their
13
C{1H}
and
31
P{1H}
NMR
spectra,
measured
in
1
H,
deuterated
chloroform.
NMR spectroscopy
The integration of signals in the
the
stoichiometry
between
the
1
H NMR spectra proved
dicarboxylic
units
and
the
phosphane ligand. The symmetry present in these compounds was
also confirmed. The
1
H NMR spectra of these complexes containe
well-resolved signals for each of the organic groups present.
Triplets were found for the methyl group of the PnBu3 ligands
at ca. 0.7 ppm with
3
JHH = 6 Hz. The protons of the methylene
units appeare as multiplets between
1.1 -1.8 ppm. All protons
for the linking unit E (eq. 17) could be detected; chemical
44
Theoretical Section
shifts and coupling constants correspond to the values typical
for such group [63-65].
The
13
C{1H} NMR spectra of 16a – 16f show signal patterns
which are characteristic for the carbon atoms of the PnBu3 and
dicarboxylic
entities.
The
methylene
group
of
PnBu3 ligand
appeared as doublet with coupling constants (1JCP = 4 - 5 Hz,
2
JCP = 10 - 14 Hz,
3
JCP = 11 - 23 Hz). For complexes 16a and 16c
- 16e only some of these coupling constants were found. The
chemical shifts and coupling constants found are close to the
values found in the literature [63-66].
The
31
P NMR spectra of 16a - 16f consist of broad signals.
These signals are shifted downfield when compared to the free
phosphane ligand (Table 19).
Table 19: Comparison of the chemical shift of the
31
P NMR
signals 16a-16f with PnBu3.
Compd.
δ[ppm]
Compd.
δ[ppm]
PnBu3
-32.4
PnBu3
-32.4
16a
-6.8
16d
-14.3
16b
-9.5
16e
-4.6
16c
-7.8
16f
-11.0
These results shows that the values move upfield towards
the value of the free phosphane ligand, with increasing of
coordination number.
45
Theoretical Section
3.5.2 TG and DSC studies of [(nBu3P)mAgEAg(PnBu3)m] complexes
The TG data of 16a - 16d are presented in table 20, while
the TG trace of 16c is examplary shown in Figure 14.
Table 20: TG data of complexes 16a-16d.
Compd.
step
Tbegin [°C]
Tend [°C]
∆mexp [%]
∆mtheo [%]
16a
1
100
315
79.27
80.85
16b
1
99
356
85.72
85.91
16c
1
125
480
80.62
81.09
16d
1
101
349
83.89
86.04
Tbegin = Temperature at the beginning of decomposition.
Tend =
Temperature at the end of decomposition.
∆mexp = Experimental value of weight loss.
Weight (%)
∆mtheo = Theoretical value of weight loss.
100
∆m
50
=
80.62
%
0
20
220
420
620
Temperature (°C)
Figure 14: TG trace of 16c (heating rate, 8 °C/min).
Results obtained reveal that complexes 16a-16d decompose
in one step.
46
Theoretical Section
The difference ∆m = ∆mexp - ∆mtheo correspond to –1.58 %
(16a), –0.19 % (16b) and –0.47 % (16c). For complex 16d this
difference resembles to 2.15 %. In this case the material left
back contains carbon impurities.
DSC studies were carried out with 16a – 16f. As example
figure 15 present the DSC trace of 16d.
Heat (mV)
40
30
20
10
0
20
120
220
320
420
520
Temperature (°C)
Figure 15: DSC trace of 16d (heating rate, 8 °C/min).
The DSC trace of 16d gives rise to two peaks which are
close to each other: one endothermic peak at 264 °C with ∆H =
-86.6 J/g and one exothermic peak at 273 °C with ∆H = 41.41
J/g. This fact could be attributed to the vaporisation of the
complex follow by a decomposition.
47
Theoretical Section
4 Synthesis of Silver Schiff-base complexes of type:
[(nBu3P)mAg{O-2-(C6H4)C(H)N(C6H4)-4-R}] (R = OMe, Me;
m = 1, 2)
Schiff-bases can successfully be used as chelating ligands
in
coordination
applications
synthesis
chemistry
in,
for
[77,78]
Schiff-base
[74].
example,
and
transition
They
catalysis
biochemistry
metal
have
[75,76],
[79,80].
complexes
potential
can
organic
Furthermore,
be
used
as
CVD
precursors in material sciences [81]. Thus, phosphan silver(I)
Schiff-base complexes were synthesized in order to investigate
their suitability as CVD precursor in the deposition of Ag.
4.1 Synthesis of Silver(I) Schiff-base Complexes
The
synthesis
of
silver(I)
Schiff-base
complexes
was
carried out in a two steps synthesis procedure. Firstly, the
respective Schiff-base ligand is synthesized using the most
common method for the preparation of imine by the reaction of
aldehyde
with
amine
[71].
In
this
respect
a
mixture
of
equimolar amount of 2-hydroxybenzaldehyd and P-anisidine or Ptoluidine dissolved in absolute ethanol was refluxed at 100 °C
for 4 h (equation 17). Products 19a and 19b were isolated by
crystallisation as green (19a) or yellow (19b) solids.
OH
OH
+
H2N R
Ethanol
C O
17
R=
H
+ H2O (17)
Reflux
C
R
H 19a, 19b
18
OCH3 ;
N
CH3
48
Theoretical Section
The synthesis of the corresponding silver(I) salts was
possible
by
equimolar
reacting
amount
of
ethanol/acetonitrile
these
Schiff-bases
[AgNO3]
in
the
mixture
(6
:
molecules
presence
1)
at
of
0
with
an
NEt3
in
°C.
After
appropriate work-up (equation 18) the silver salts 20a and 20b
could be isolated as light sensitive solids.
OH
O
+
C
N
NEt3
[AgNO3]
(18)
-HNEt3+NO3C
R
H 19a, 19b
Ag
N
R
H 20a, 20b
2
Complexes 20a and 20b are poorly soluble in most common
polar organic solvents such as DMSO or DMF. Therefore, they
could be only characterized by IR spectroscopy and elemental
analysis. However the solubility of complexes 19a and 19b in
deuterated chloroform enabled the characterization of these
compounds by 1H- and
13
C-NMR.
4.1.1 Spectroscopic studies
IR Spectroscopy
The IR spectra (Table 21) of compounds 19 and 20 exhibit
the
charateristic
C=N
stretching
vibration.
While
the
stretching frequencies of the OH group did not appear in the
IR spectra of compounds 19a and 19b, due to the formation of
hydrogen bonds between the protons of the OH group and the
nitrogen atom.
49
Theoretical Section
Table 21: Selected IR data of 19 and 20.
The
IR
Compound
νC=N(cm-1)
νC=C(cm-1)
19a
1622
1570
19b
1617
1597
20a
1622
1567
20b
1618
1567
spectra
of
these
compounds
exhibit
the
characteristic C=N stretching vibration at ca. 1600 cm-1 which
is typical for a imine group. νC=C stretching frequencies for
the phenyl groups are found between 1560 - 1600 cm-1.
NMR Spectroscopy
1
H NMR of 19a and 19b contain sharp and well-resolved
signals
for
each
of
the
organic
group
present.
OH
Proton
appears at 13.41 ppm. The methoxy group in 19a resonates at
3.84 ppm. For 19b signal of the methyl group was observed at
2.39 ppm. The protons of the phenyl group could be detected as
multiplet between 6.90 - 7.40 ppm.
13
The
C spectrum NMR of 19a shows a signal at 55.95 ppm
for the methoxy group, while the respective methyl group of
19b resonates at 21.40 ppm. The carbon atom of the imine group
can
be
detected
at
161.4
(19a)
and
162.10
(19b)
ppm.
The
phenyl groups show their Resonances in the range 117 - 161
ppm.
Chemical
compounds
19a
shifts
and
literature [63-66].
found
19b
are
in
1
H-
close
and
to
13
C-NMR
those
spectra
found
in
of
the
50
Theoretical Section
4.2 Synthesis of the
n
Bu3P Silver(I) Schiff-base of type
[(nBu3P)mAg{O-2-(C6H4)C(H)N(C6H4)-4-R}]
The synthesis of phosphan stabilized silver(I) Schiff base
complexes was possible by addition of PnBu3 in a suspension of
silver salts 20a, 20b in diethyl ether at 25 °C (see equation
19).
O
O
Ag
Et2O
n
+ m P Bu3
C
H
N
C
N
R
H
21a: R = PhOMe, m = 1
21b: R = PhMe, m = 1
21c: R = PhOMe, m = 2
21d: R = PhMe, m = 2
4
20a, 20b
Ag
(19)
25 °C
R
[PnBu3]m
Complexes 21a - 21d are light and air sensitive. At room
temperature they can be stored for two days. However for a
long
period
possible
of
time
they
decomposition.
were
stored
Complexes
21a
at
–30
and
21b
°C
to
are
avoid
solids,
while complexes 21c and 21d are liquids.
4.2.1 Spectroscopic studies
IR Spectroscopy
The
IR
spectra
of
complexes
21a
-
21d
show
the
characteristic νC=N and νC=C stretching frequencies. Selected IR
data of these compounds are given in Table 22.
The data obtained correspond to this type of structure
motif.
51
Theoretical Section
Table 22: Selected IR data of 21a - 21d
νC=N(cm-1)
νC=C(cm-1)
21a
1618
1573
21b
1618
1598
21c
1610
1502
21d
1595
1508
Compound
NMR Spectroscopy
1
The
H-NMR spectra of complexes 21a - 21d consist of well-
resolved signals for each of the organic groups present (C6H4,
PnBu3, OCH3, CH3 and CH=N). The methyl group of the
the phosphan ligand appears at ca. 0.8 ppm with
3
n
Bu3 unit of
JHH = 6 - 7Hz,
whereas the methylene protons can be detected as multiplet
between 1.2 - 1.6 ppm. The OCH3 group in 21a and 21c gives rise
to a singlet at 3.8 ppm, while in 21b and 21d CH3 group is
found at 2.3 ppm. The multiplets at 6.1 - 7.4 ppm can be
assigned to the protons of C6H4 group. The hydrogen atom of the
CH=N group appear at ca. 8 ppm.
13
The
C{1H} NMR spectra of 21a - 21d show the expected
signal pattern for each group. The CH2 entities of the PnBu3
phosphan ligand gives rise to three doublets at ca. 24, 25 and
28 ppm with coupling constants
Hz and
3
JCP = 12 - 14 Hz,
2
JCP = 11 - 19
1
JCP = 5 - 6 Hz. The CH3 entities appear as singlet at
ca. 13 ppm. The OCH3 and CH3 groups of the Schiff-base ligands
are found at ca. 55 and 20 ppm, respectively. For the C=N unit
the
13
C{1H} NMR signal is found between 160 - 175 ppm.
In the
31
P-NMR spectra of complexes 21a - 21d signals are
shifted downfield, when compared to the free phosphan ligand
PnBu3. For 21a two doublets at –1.7 ppm with the coupling
constant
1
J107Ag31P = 729 Hz and
1
J109Ag31P = 648 Hz are observed,
52
Theoretical Section
1
while 21b resonates at –2.8 ppm as a broad doublet with
JAg31P
= 673 Hz. These results can be ascribed by a intermolecular
exchange of phosphane ligand in these complexes [36,55,67].
For complexes 21c and 21d broad signals are found at –8.1 and
–9.5.
4.2.2 Solid-State Structures of 21a and 21b
Preamble:
a
containing
wide
range
Schiff-base
characterized
by
of
transition
ligands
single
X-ray
have
metal
been
structure
complexes
structurally
determination
and
different arrangements of this group around the metals were
found [82-87].
Cadmiun(II) complexes of Schiff base ligands derived from
tripodal
capped
atom
tetraamines
distorted
[82].
and
trigonal
Iron(III)
2-acetylpyridine
antiprism
complexes
possess
geometry
with
a
around
monothe
salicylaldimine
Cd
ligand
confere a distorted octahedron environment around Fe(III) ion
[83]. Imine-ether ligands coordinate in a tetradentate manner
around Ag(I) ions, which gives rise to a distorted tetrahedral
arrangement [84]. Furthermore, a trigonal planar coordination
sphere
was
found
in
Cu(I)
complexes
with
a
Schiff-base
containing a triazole ligand [85]. Zinc complexes featuring a
tripodal
imine-phenol
bipyramidal
geometry
ligand
[86].
possess
The
a
reaction
distorted
of
trigonal
diorganotin(IV)
dinitrates with nickel, cobalt and zinc Schiff base complexes
give
compounds
containing
tin
in
a
pentagonal
bipyramidal
environment set-up by four Schiff-base oxygens and a nitrate
oxygen atom[87].
53
Theoretical Section
Solid State structure of 21a
Single crystals suitable for the X-ray structure analysis
could be obtained by crystallisation of 21a in diethyl ether
at
–30
°C.
Figure
15
presents
the
molecular
structure
of
complex 21a. Interatomic bond distances [Å] and angles [°] are
summarized in Table 23.
Figure 16: Molecular structure of 21a, the hydrogen atoms have
(Probability of thermal
been omitted for clarity
ellipsoids: 50%).
Complex 21a crystallises in the triclinic space group P-1
as a centrosymmetric dimer. The main structural feature is the
central Ag(1)-O(1)-Ag(1A)-O(1A) square. The Ag2O2 ring lies in
plane;
torsion
angles
N(1)-Ag(1)-O(1)-C(1)
and
P(1)-Ag(1)-
O(1)-C(1) equal to 29.6 (2) ° and -119.3 (2) ° were found. A
similar
Ag2O2
structures
four
analysis
membered
of
ring
complex
was
11c
found
and
in
the
other
x-ray
silver(I)
complexes, like [Ag2(picl)2(H2O)2H2O] [88]. Silver is further
coordinated
by
the
nitrogen
of
the
pyridyl
group
and
the
phosphorus atom of the tri-n-butylphosphan ligand, thus the
54
Theoretical Section
geometry around Ag is a distorded tetrahedral. A six membered
ring is built up by Ag(1), O(1), C(1), C(6), C(7) and N(1).
Following
Ag(1)-p(1)
These
bond
2.3479
distances
structures
lengths
of
were
(8),
are
found:
Ag(1)-N(1)
shorter
other
Ag(1)-O(1)
2.314
than
those
silver(I)
(2)
Å
found
2.3048
(Table
in
complexes
(19),
23).
crystal
such
as
[Ag{N(O)C(CN)2}(PPh3)2] [89],[Ag(PPh3)(C9H7NO)-(C9H6NO)] [90] and
[Ag(PPh3)2{ONC(CN)COPh}] [91]. This could be ascribed to an
effect
of
the
formation
of
the
Schiff-base
chelat
ring
involving a strong van der Waal´s interaction. The bond length
C(7)-N(1)
1.291
(4):
is
in
the
range
described
in
other
Schiff-base ligands such as N-salicylidene-2-aminopyridine and
N-(o-hydroxyphenyl)-5-methoxysalicylaldimine [92,93].
Solid State structure of 21b
Single crystals suitable for the X-ray structure analysis
could be obtained by crystallisation of 21b in diethyl ether
at –30 °C. Figure 17 presents the molecular structure of 21b.
Figure 17: Molecular structure of 21b, the hydrogen atoms have
been omitted for clarity
ellipsoids: 50%)
(Probability of thermal
55
Theoretical Section
Complex
significant
21b
bond
is
isostructural
lengths
and
to
angles
complex
are
21a.
All
similar.
The
difference between these two structures is the fact that for
21a the phenyl ring of the schiff base ligand is substituted
by a methoxy group instead of a methyl group as in 21b.
Table 23: Selected bond distances [Å] and angles [°] of 21a
and 21b
Bond distances [Å]
Complex 21a
Complex 21b
Ag(1)-O(1)
2.305 (2)
2.310 (4)
Ag(1)-P(1)
2.348 (8)
2.346 (2)
Ag(1)-N(1)
2.314 (2)
2.321 (5)
O(1)-C(1)
1.296 (3)
1.296 (7)
C(7)-N(1)
1.291 (4)
1.284 (8)
Bond angles [°]
O(1)-Ag(1)-N(1)
79.8 (8)
79.4 (2)
O(1)-Ag(1)-O(1A)
91.5 (6)
90.3 (1)
N(1)-Ag(1)-P(1)
138.9 (6)
137.4 (1)
Ag(1)-O(1)-Ag(1A)
88.5 (6)
89.7 (1)
N(1)-C(7)-C(6)
128.6 (3)
128.0 (7)
a) The estimated standard deviation of the last significant
digits are shown in parentheses.
4.2.3 TG and DSC studies
The thermal behaviour of 21a – 21d was studied by TG and
DSC analysis. The TG data are summarized in Table 24. Figure
18 shows TG trace of 21c.
56
Theoretical Section
Table 24: TG data of complexes 21a - 21d
Compound
step
Tbegin [°C]
Tend [°C]
∆mexp [%]
∆mtheo [%]
21a
1
102
519
73.10
79.89
21b
1
153
401
73.45
79.27
21c
1
107
499
81.14
85.39
21d
1
101
400
83.36
85.07
Tbegin = Temperature at the beginning of decomposition.
Tend =
Temperature at the end of decomposition.
∆mexp = Experimental value of weight loss.
Weight %
∆mtheo = Theoretical value of weight loss.
100
80
60
40
20
0
∆m
20
220
420
=
81.14
%
620
Temperature (°C)
Figure 18: TG trace of 21c (heating rate, 8 °C/min).
Results obtained reveal that the decomposition of these
silver(I) complexes occur in one step. Thus it is difficult to
propose a decomposition mechanism for these compounds, this
could be attributed to the high temperature ramp.
The difference ∆m = ∆mexp - ∆mtheo is –6.79 % (21a), -5.82 %
(21b), -4.25 % (21c) and –1.71 % (21d).
57
Theoretical Section
Complexes
Differential
–
21a
Scanning
21d
were
Calorimetry.
also
Figure
characterized
19
presents
by
the
result obtained for complex 21b.
Heat (mV)
30
10
-10
10
110
210
310
410
-30
Temperature (°C)
Figure 18 DSC trace of 21b (heating rate, 8 °C/min).
Two
peaks
were
found
in
the
DSC-curve
of
21b.
one
endothermic peak at 89 °C and one exothermic peak at 218 °C
with ∆H equal to 12.01 J/g and -68.96 J/g.
TG and DSC studies give a first idea on the decomposition
pattern
of
the
above
described
silver(I)
complexes.
Nevertheless, gas phase study is the core to understand the
process occuring during the formation of the film. For this
reason, selected compounds were further investigated by mass
spectrometry in order to elucidate the gas phase decomposition
mechanism of these silver CVD precursors.
58
Theoretical Section
5 Mass spectrometric Investigations
The
volatility
synthesized
and
silver(I)
temperature-programmed
the
thermal
complexes
and
stability
were
in-situ
of
the
investigated
using
time-of-flight
mass
spectrometry. This work was performed in collaboration with
the research group of Prof. Dr. Katharina Kohse-Höinghaus at
the University of Bielefeld (Germany), (partner Thomas haase).
5.1 Temperature-programmed Mass Spectrometry
Complexes
10d,
10b,
10e,
and
16b
21c
have
been
investigated with temperature-programmed mass spectrometry to
obtain information about their volatility. These experiments
was carried in order to detect silver containing fragments in
the gas phase, which is the first selection criterion for the
CVD precursors.
The
completely
compounds
were
evaporated
dissolved
during
the
in
first
acetone
minutes.
which
was
Then
the
temperature was increased at a ramp of 20 K/min from 300 to
900 K. All these complexes liberate the phosphin ligand (nBu3P)
which is detected through the signal of mass m/z = 202; the
subsequent fragments are discussed below.
The decomposition processes of 10d, 10b, 10e, 16b and 21c
was analysed in detail. Results obtained have been reported
[94].
An overview of all measured signals is given in Table 25a
–25d.
59
Theoretical Section
Table 25a: Intensities in temperature-programmed mass spectra
of
complex
containing
to the
107
10d;
100
fragments,
%
only
is
C3H9P.
signals
For
silver-
corresponding
Ag isotope are listed.
Temperature (K)
465
585
635
m/z
%
%
%
C12H27P-Ag
309.09
0.00
5.61
1.50
C16H37AgP
364.14
0.00
0.30
0.00
Ag
106.91
0.00
0.10
0.00
C5H8O2
100.05
4.29
11.89
7.89
C5H7O
83.05
3.29
12.97
5.88
CO2
44.00
0.00
1.34
1.63
C4H7
55.05
24.90
36.52
29.66
C2H6P
61.02
25.46
25.11
24.88
C2H7P
62.03
64.38
64.13
57.20
C3H9P
76.04
100.00
100.00
100.00
C4H10P
89.05
11.64
11.53
10.87
C5H13P
104.08
38.32
39.85
33.28
C6H15P
118.10
29.07
30.27
25.69
C7H16P
131.10
22.00
22.86
19.94
C8H19P
146.12
18.41
20.37
16.33
C9H21P
160.14
6.34
6.73
5.81
C10H22P
173.15
46.29
50.66
42.52
C12H27P
202.19
24.81
26.87
21.10
n
(- Bu3P)
60
Theoretical Section
Table 25b: Intensities in temperature-programmed mass spectra
of
complex
containing
to the
107
10b;
100
fragments,
%
is
only
C3H9P.
For
signals
silver-
corresponding
Ag isotope are listed.
Temperature (K)
435
535
615
745
m/z
%
%
%
%
C12H27P-Ag
309.09
0.00
0.65
2.47
0.00
C8H8O2
C7H7
136.03
91.04
18.04
60.89
13.32
47.93
7.90
78.66
1.56
5.71
CO2
C4H7
44.00
55.05
1.72
22.18
2.76
24.30
4.96
26.54
7.61
27.92
C3H9P
C12H27P
(-nBu3P)
76.04
202.19
100.00
28.75
100.00
30.59
100.00
36.72
100.00
24.29
Table 25c: Intensities in temperature-programmed mass spectra
of
complex
containing
to the
107
10e;
100
fragments,
%
only
is
C3H9P.
signals
For
silver-
corresponding
Ag isotope are listed.
Temperature (K)
m/z
563
%
703
%
803
%
C12H27P
(-nBu3P)
C10H22P
C3H9P
202.19
23.12
23.94
5.98
173.15
76.04
43.51
100.00
44.09
100.00
10.10
100.00
CO2
C2H4O2
C3H5O2
43.99
60.02
73.03
1.44
15.29
17.83
3.03
42.93
47.21
5.31
70.81
78.00
C6H13
85.10
5.16
15.18
31.45
C9H17O2
C12H23O2
n
Bu3P-Ag
157.02
200.18
309.09
4.76
4.23
0.00
12.85
11.52
1.00
20.54
19.72
0.00
61
Theoretical Section
Table 25d: Intensities in temperature-programmed mass spectra
of complex
21c; 100 % is C3H9P.
Temperature (K)
523
633
753
C12H27P (- Bu3P)
m/z
202.19
%
26.64
%
19.60
%
23.37
C10H22P
C3H9P
CO2
173.15
76.04
44.00
45.35
100.00
0.00
38.98
100.00
0.00
43.22
100.00
0.00
C14H14NO
C14H13NO2
212.00
227.09
58.00
96.59
54.65
96.50
47.13
78.38
n
For complex 10d the fragment C16H37Pag+ (m/z = 364) is seen
with low intensity compared to the fragment at m/z = 309,
which represents a AgPnBu3+, silver (m/z = 107). The fragments
at
m/z
=
189,
173,
160,
146,
131,
104,
89,
76
and
62
correspond to the fragmentation of PnBu3 (m/z = 202) under
electron beam effect [95]. The fragment at m/z = 55 (C4H7+) can
be assigned to both the phosphine as well as the carboxylate
part of the complex. An increase in temperature favors the
evaporation of the complex, which is expressed by a general
increase in all peak intensities. A maximun is observed and
then
all
intensities
decrease
gradually,
which
express
the
complete evaporation of the substance. This behaviour confirms
the stability and the good volatilty of this complex. The
examination of the detected fragments allows the proposition
of the decomposition mechanism that occurs during ionization
with
the
electron
beam
in
the
decomposition paths are plausible:
mass
spectrometer.
Two
62
Theoretical Section
OOC
H
C
n
Bu3P
n
Ag
C
H3C
Ag +
Bu3P
n
m/z = 309
H
C
Bu3P
n
+
H3C
CH3
m/z = 100
1
AgOOC
C
Bu3P
m/z = 202
n
+
m/z = 107
Bu3P
m/z = 202
CH3
2
n
Bu3P
10d
CO2
n
+
m/z = 44
Bu3P
Ag
H
C
+
C
H3C
CH3
m/z = 364
m/z = 202
H
n
Bu3P
Ag
+
m/z = 309
Ag
C
n
+
m/z = 107
C
H3C
CH3
m/z = 55
Bu3P
m/z = 202
The first one corresponds to the elimination of one
n
Bu3P
ligand and the O2CCMe=CHMe unit. The fragment formed in this
case
is
n
Bu3PAg
(m/z
=
309).
Further
decomposition
of
the
carboxylic unit gives CO2 and C4H7. However, the second path
assumes the elimnation of one phosphan ligand and a selective
elimination of CO2, forming a direct Ag-C bond (m/z = 364),
which is then broken to form a stabilized silver-ion with one
phosphan ligand (m/z = 309).
Another
type
decomposition
of
of
behaviour
complex
10b
is
presented
by
the
[(nBu3P)2AgOOCCH2Ph].
For
this
compound the detected fragments are summarized in Table 25b.
Silver-containing fragments (m/z = 309), PnBu3+ fragments (m/z
= 202), carboxylic fragments (m/z = 91 and m/z = 136, benzene
acetate)
could
be
detected.
The
fragmentation
path
during
ionization with electron beam is discussed below. However, the
phosphane
ligand
and
the
benzene
acetate
showed
a
second
maximun peak at higher temperatures, while no trace of silvercontaining
consistent
fragments
with
an
was
eventual
observed.
This
decomposition
evaporator, forming silver residues.
observation
of
10b
in
is
the
63
Theoretical Section
Temperature-programmed mass spectrometric studies with the
silver dicarboxylate 16b [(nBu3P)3AgOOCCH2COOAg(PnBu3)3] did not
present any volatile silver-containing fragments. Out of this
reason
it
is
not
recommended
for
the
CVD
process
using
conventional evaporation techniques. Nevertheless, its ability
to decompose to silver residue may offer other interesting
applications in wet-coating processes, such as spin coating,
dip coating or aerosol-assisted CVD.
Mass
spectrometric
investigations
carried
out
on
10e
[(nBu3P)2AgOOC(CH2)10CH3] showed that silver-containing fragments
(m/z = 309) are seen in low intensity at ca 703 K. However,
signals derived from the carboxylate entity will m/z = 60
(C2H4O2),
m/z
=
73
(C3H5O2+),
m/z
=
85
(C6H13+),
m/z
=
157
(C9H17O2+) and m/z = 200 (C12H23O2+) increase in 563 - 803 k
range. A complete evaporation of the complex was assigned to
the disappearance of the silver-containing fragment signal.
Following decomposition mechanism is proposed:
n
Bu3P
AgOOC(CH2)10CH3
n
n
Bu3P
Ag
m/z = 309
Bu3P
n
+
Bu3P
+ O2C(CH2)10CH3
m/z = 202
m/z = 200
10e
+
Ag
m/z = 107
n
Bu3P
m/z = 202
O2C(CH2)8
C6H13
O2C3H5
m/z = 157
m/z = 85
m/z = 73
CO2
C2H4O2
m/z = 44
m/z = 60
No volatile silver-containing fragments were found during
the
temperature-progammed
mass
spectrometric
studies
of
n
complex 21c [( Bu3P)2Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}]. This could
be
ascribed
Schiff-base
to
the
complex
high
which
molecular
hinders
weight
the
of
this
transport
silver
of
the
substance in the gas phase. The imine function might also
64
Theoretical Section
induce
intermolecular
reactions
forming
non-volatile
molecules.
5.2 In-situ time-of-flight Mass Spectrometry
The thermal instability of complex 10b expresses its high
ability to react in the gas phase during the transport to the
hot surface of the substrate, where deposition takes place.
The CVD conditions were thus reproduced in a molecular beam
TOF-mass spectrometer in order to investigate the gas phase
behaviour
of
significant
complex
starting
equilibrium.
The
10b.
at
Evaporation
=
Tevap
evaporation
425
was
K
temperature
observed
in
was
to
be
thermodynamic
kept
constant
(Tevap = 425 K), and the pressure in the CVD reactor was kept at
50 mbar, while the reactor temperature varied between 425 and
725 K. When the temperature in the reactor is set equal to
that
of
the
evaporation,
temperature-programmed
the
same
fragments
as
in
the
mass spectrometry were detected. With
the assumption that the ionization efficiency is independent
of the temperature of the molecular beam, it can be concluded
that
the
observed
increase
is
related
to
the
thermal
decomposition that presents, in this case, the same fragments
as those observed during the electron beam ionization were
found. Therefore, the thermal decomposition in the gas phase
is expected to occur by a similar path.
n
Bu3P
O
Ag
n
Bu3P
O
C CH2
10b
n
O
Bu3P
Ag
+
m/z = 309
n
Bu3P
m/z = 202
O
+
C CH2
Ag
m/z = 107
CO2
m/z = 44
+
Bu3P
m/z = 202
m/z = 136
+
n
CH2
m/z = 91
65
Theoretical Section
At high temperatures (555 - 725 K), the intensity of the
detected
fragments
decreases,
which
is
consistent
with
a
decomposition of the complex on the wall of the CVD reactor,
resulting in silver deposit and small molecules as byproducts.
Thus, in-situ mass-spectrometry performed under CVD conditions
permits the elucidation of the gas phase thermolysis mechanism
of complex 10b.
The study of the fragments intensity as a function of the
reactor
temperature
reveals
that
this
complex
could
be
transported in the gas phase in the temperature range of 425 –
555
K,
because
the
intensity
of
the
silver-containing
fragment signal is high in this region (figure 20).
202
173
139
91
60000
55000
50000
309
2600
2400
45000
Intensity [w.E.]
2800
2200
40000
2000
35000
1800
30000
1600
25000
20000
1400
15000
1200
10000
1000
5000
150
200
250
300
350
400
450
Tem perature [°C]
Figure 20: Intensity of
fragments as a function of reactor
temperature of 10b.
The
results
obtained
from
mass
spectrometric
investigations reveal that phosphane silver carboxylates are
stable
in
the
gas
phase
dicarboxylates
are
not
[50,94,96].
recommended
While
for
CVD
phosphan
process
silver
using
conventional evaporation techniques. However, phosphan silver
schiff-base complexes were unstable in the gas phase. Thus,
Theoretical Section
66
CVD experiments were performed with a pulsed spray evaporation
system using phosphan silver carboxylates and dicarboxylates
as precursors.
67
Theoretical Section
6 CVD Experiments
Deposition experiments were performed using a cold-wall
CVD
reactor
with
a
pulsed
spray
evaporation
system.
This
method has several advantages for precursor delivery. With a
suitable solvent a wide variety of precursor compounds can be
used, including solids and other compounds not suitable for
vapor delivery [97,98]. Silver films were deposited on glass
substrates using 10b, 10d, 10e and 16b as precursors.
6.1 Device Description
The system allows to inject the respective liquid complex
as
pulsed
spray
in
the
evaporation
chamber.
A
schematical
illustration of the experimental set-up is shown in figure 21.
Figure 21: Schematic CVD reactor configuration.
A liquid delivery system was used to supply and vaporize
the precursor solution in the CVD reactor. The precursors are
dissolved
in
THF
and
transferred
to
a
vessel
which
is
connected to the vaporizer by a spray system. Few microliter
68
Theoretical Section
of
the
solution
is
supplyed
as
small
droplets
into
the
evaporator at each pulse. Droplets are flash evaporated and
precursor vapours as well as solvent vapours are carried by
nitrogen flow towards the substrate. The resulting by-products
are exhausted by a pumping system.
The deposition conditions used in this study are presented
in Table 26.
Table 26: Deposition conditions used in Ag CVD studies.
The
Evaporation temperature (°C)
150
Deposition temperature (°C)
250 - 400
Flow rate of N2 (Sccm)
40
Reactor pressur (mbar)
1
Injection time (ms)
2
Deposition time (min)
30 - 50
Precursor concentration (g/l)
1.2 - 3
silver
films
microscopy,
X-ray
Microscopy
(SEM).
determined.
were
characterized
diffraction
The
(XRD)
electrical
and
by
optical
Scanning
resistivity
light
Electron
was
also
69
Theoretical Section
6.2 Film characterization
X-ray Diffraction Analysis
The
(XRD).
films
were
Figure
21
analyzed
shows
with
the
X-ray
XRD
powder
spectrum
diffraction
for
the
films
deposited from complex 10d.
(1 1 1 )
intensity (cps)
Cubic modification of Ag
(2 0 0 )
(3 1 1 )
(2 2 0 )
40000
20
35000
30
40
50
60
70
80
2 θ (d e g re e s)
30000
Intensity (cps)
25000
20000
15000
10000
5000
0
-5 0 0 0
0
Figure
21:
XRD
10
20
spectrum
30
of
40
50
2 θ (d e g re e s )
silver
60
70
film
80
90
deposited
from
10d at 300 °C.
XRD analysis of silver films deposited from complex 10b,
10e
and
16c
show
similar
results.
The
comparison
of
XRD
spectra obtained with a reference XRD spectrum of cubic silver
led
us
to
conclude
that
all
these
silver
thermally stable cubic crystalline structure.
films
have
the
70
Theoretical Section
SEM Images
The microstructure and the morphology of resulting films
were
examined
by
Scanning
Electron
Microscopy.
Following
micrographes have been obtained:
Figure 22: SEM images of silver films deposited from 10b at
300 °C (left) and 325 °C (right).
Figure 23: SEM images of silver films deposited from 10d at
300 °C (left) and from 10e at 400 °C (right).
Figure 24: SEM images of silver films deposited from 16b at
250 °C (left) and 300 °C (right).
71
Theoretical Section
Scanning Electron Microscopy analysis revealed that the
silver film thicknesses were in the range of 100 – 600 nm,
while the crystallite size calculated from the XRD spectra
using Scherrer equation was in the 40 – 60 nm range. Thin
films
obtained
appearance.
SEM
under
optimal
pictures
show
conditions
that
have
smooth
a
mirror-like
structures
with
compact nanocrystallites were obtained with 10b, 10d and 10e.
However,
the
silver
dicarboxylate
16d
gives
rise
to
rough
silver films. The electrical resistance of the deposited films
was measured with the four-points probe method. Films with a
thickness superior to 200 nm indicated values in the range of
mΩ.cm.
72
Experimental Section
7. Experimental Section
This
Chapter
is
divided
Instruments
and
measurement
materials,
(7.3)
Synthesis
into
four
Sections:
conditions,
procedure
(7.2)
and
(7.1)
Starting
Experimental
data,and (7.4) Crystal refinement data.
7.1 Instruments and Measurements Conditions
General procedure
All
reaction
purified
were
nitrogen
carried
(O2
out
traces:
under
CuO
an
atmosphere
catalyst,
BASF
of
AG,
Ludwigshafen; H2O: molecular sieve 4 Å, Aldrich) using standard
schlenk
techniques.
purified
by
Tetrahydrofuran,
distillation
from
diethyl
ether
sodium/benzophenone,
were
whereas
acetonitril was purified by distillation from calcium hydride.
IR-spectra
Infrared spectra were recorded with a Perkin-Elmer FT-IR
1000 spectrometer.
NMR spectra
1
H,
13
C{1H}
and
31
P{1H}
NMR
Bruker Advance 250 spectrometer.
at 250.130 MHz,
13
spectra
1
were
recorded
31
a
H NMR spectra were recorded
C{1H} NMR spectra at 62.895 MHz and
NMR spectra at 101.255 MHz.
on
31
P{1H}
P{1H} NMR spectra: CDCl3 with
P(OMe)3 as external standard [δ = 139.0, rel. to H3PO4 (85 %),
δ = 0.0 ppm]. Chemical shifts are reported in δ units (parts
per million) downfield from tetramethylsilane with the solvent
as the reference signal (1H: CDCl3, δ = 7.26 and d6-DMSO, δ =
2.49;
13
C{1H}: CDCl3, δ = 77.0 and d6-DMSO, δ = 39.7).
73
Experimental Section
Melting point
Melting
points
were
determinated
using
sealed
nitrogen
purged capillaries on a Büchi Mp 510 melting point apparatus
and are uncorrected.
Elemental Analysis
Microanalysis were peformed by the Institut of Organic
Chemistry, TU Chemnitz and partly by the Institut of Organic
Chemistry, University Heidelberg.
TG and DSC Analysis
The thermal analysis was conducted with the Pyris TG / DSC
system (Perkin-Elmer) under the following conditions: heating
rate, 8 °C/min, atmosphere, N2 20 L/h; analysis using Pyris
software.
Single crystal X-ray Diffraction Analysis
Generality:
For
data
collection
a
Single
crystal
diffractometer of the type SMART 1k of the company Bruker axs,
equipped
with
monochromator.
a
The
CCD
detector
preparation
of
and
the
M0-Kα
a
single
graphite
crystals
took
place under a Perfluorpolyalkylether of the company ABCR for
the
ST.)
protection
[99].
against
For
the
oxygen
and
measurement
humidity
of
(viscosity
1600
temperature-sensitive
substances a LT2 low temperature device was used, for the
cooling
of
temperatures
according
to
single
to
-80
the
crystals
°C.
All
Patterson
with
liquid
structures
method
or
were
by
nitrogen
solved
means
of
on
either
direct
methods with SHELXS NT V5.1 [100]. The structures were then
refined by the least squares method based on F2 with SHELXS NT
V5.1 [101].
The pictures of the molecules were drawn with the programs
ORTEP [102] and POV Ray. All non hydrogen atoms were refined
74
Experimental Section
in the positions they were found. The hydrogen atoms were set
into the positions computed to their neighbouring atoms and
refined dependently on its position and thermal parameters as
so-called "riding model". Hydrogen atom positions at relevant
structure
units
are
inferred
from
the
difference
Fourier
synthesis and refined freely.
The indicated R-values are defined as follows:
R1 = [∑(||F0|-|Fc||)/∑|F0|]; wR2 = [∑(w(F02-Fc2)2/∑(wF04)]1/2;
W =[σ2(F02) + (g1P)2 + g2P]-1; P = [max(F02,0) + 2 Fc2]/3
Defects: In the structures some defects arose, as for example
the twist or rotation defect of remainders of the phosphane or
phosphite
components.
For
the
refinement
of
false
arranged
structures certain defaults were used. The SAME instruction
adapts the distances 1,2 and 1,3 from chemically equivalent
groups
with
an
effective
standard
deviation.
The
SADI
instruction adapts the 1,2- bonds with an effective standard
deviation. The SIMU instruction adapts the Uij of neighbouring
atoms
with
an
effective
standard
deviation
and
the
DELU
instruction adapts components of the anisotropic displacement
parameters
toward
the
bond
with
an
effective
standard
deviation.
Temperature-Dependent Mass Spectrometry
The
temperature-programmed
mass
spectra
were
recorded
using an autospec X magnetic sector mass spectrometer with EBE
geometry (Vacuum Generators, Manschester, UK) equiped with a
standard
electron
beam
ionization
source.
Samples
were
dissolved in acetone (ratios 1:10 – 1:100) and introduced by
push
rod
evaporated
mbar),
in
aluminium
completely
heating
was
crucibles.
under
set
at
vacuum
a
ramp
When
the
conditions
of
20
acetone
had
(10-5
–
10-6
The
gas
K/min.
ionization, above the aluminium crucible, was performed using
75
Experimental Section
an
electron
beam
with
an
energy
of
70
eV,
and
the
ions
produced were accelerated by a potential energy of 8 KV. The
spectra were recorded and processed with Opus software.
In-situ Mass Spectrometry
For the in-situ mass spectrometry a molecular beam was
extracted through a quartz nozzle from the deposition zone of
a reactor, expanded and investigated in a time-of-flight mass
spectrometer. The precursors were evaporated and transported
to the deposition zone (heated quartz tube, length 100 mm) at
a pressure of 50 mbar. Argon was used as the carrier gas at a
flow of 100 sccm. The electron impact ionization took place at
a pressure between 10 - 6 mbar and at an ionization energy of
30
eV.
More
details
of
this
set-up
can
be
found
in
the
literature [50].
CVD
The CVD experiments were performed in a vertical cold-wall
reactor with stagnation-point-flow geometry. The precursor was
dissolved
in
tetrahydrofuran
and
introduced
to
the
reactor
using a pulsed spray evaporation technique that allows the
control of the feeding rate between 0.5 and 20 mL/min. The
precursor solution was mixed to pre-heated flow of nitrogen in
the heated evaporation chamber. The inlet tube, with an inner
diameter of 10 mm, was maintained at a temperature slightly
above the evaporation temperature to prevent condensation. The
glass substrates were cleaned with hot sulfuric acid, acetone,
and ethanol in an ultrasonic bath and placed on a resistively
heated
ceramic
block.
The
temperature
was
measured
with
a
thermocouple locate directly at the substrate. A rotary oil
pump equiped with a cooling trap was used to keep the reactor
system at a pressure of 1 mbar during the deposition process.
The
precursor
analytical
solutions
quality
and
were
the
made
nitrogen
with
tetrahydrofuran
carrier
gas
was
in
dried
76
Experimental Section
before use. The evaporation temperature used was 425 K, the
deposition temperature range was 525 – 675 K. The deposition
time was 30 – 50 min range with a pressure of 1 mbar. The flow
rate
of
the
carrier
gas
was
40
sccm
nitrogen
and
the
concentration of the precursor solution in tetrahydrofuran was
between 1.2 g/L and 3 g/L. The thickness of the films was
estimated gravimetrically assuming that the deposit has the
density of bulk silver. The films were inspected using optical
microscopy
(Leica
DM
LM,
magnification
1500),
and
analyzed
with X-ray diffraction (XRD) (X´pert pro MRD, Phillips) and
scanning
electron
microscope
(SEM)
(Hitachi
S-450).
The
electrical resistivity was measured using a home-built fourpoint probe set-up.
7.2 Starting materials
n
Bu3P
was
atmosphere,
calcium
purified
while
hydride.
Net3
All
by
was
other
distillation
purified
by
chemicals
under
nitrogen
distillation
were
commercial providers and were used as received.
purchased
from
by
77
Experimental Section
7.3 Synthesis Procedures and Experimental Data
Outline of synthesized compounds
7.3.1
Synthesis of [AgO2CtBu] (3a)
79
7.3.2
Synthesis of [AgO2CCMe2(OH)] (3b)
79
7.3.3
Synthesis of [AgO2CCH2Ph] (3c)
80
7.3.4
Synthesis of [AgO2CCHPh2] (3d)
80
7.3.5
Synthesis of [AgO2CCMe=CHMe] (3e)
80
7.3.6
Synthesis of [AgO2C(CH2)10CH3] (3f)
81
7.3.7
Synthesis of [AgO2C(C4H3O)] (3g)
81
7.3.8
Synthesis of [AgO2CCH=CH(C4H3O)] (3h)
82
7.3.9
Synthesis of [AgO2CC(O)CH3] (3i)
82
7.3.10
Synthesis of [AgO2CC(O)CH2CH3] (3j)
82
7.3.11
Synthesis of [AgO2CCH2CO2Ag] (3k)
83
7.3.12
Synthesis of [AgO2CCH2CH2CO2Ag] (3l)
83
7.3.13
Synthesis of [AgO2C(C4H3S)CO2Ag] (3m)
84
7.3.14
7.3.15
n
t
Synthesis of [(P Bu3)AgO2C Bu] (7a)
84
n
85
n
Synthesis of [(P Bu3)AgO2CCH2Ph] (7b)
7.3.16
Synthesis of [(P Bu3)AgO2CCHPh2] (7c)
86
7.3.17
Synthesis of [(PnBu3)AgO2CCMe=CHMe] (7d)
87
7.3.18
7.3.19
n
88
n
88
n
Synthesis of [(P Bu3)AgO2C(CH2)10CH3] (7e)
Synthesis of [(P Bu3)AgO2C(C4H3O)] (7f)
7.3.20
Synthesis of [(P Bu3)AgO2CC(O)CH3] (7g)
89
7.3.21
Synthesis of [(PnBu3)AgO2CC(O)CH2CH3] (7h)
90
t
7.3.22
Synthesis of [{P(OMe)3}AgO2C Bu] (8a)
91
7.3.23
Synthesis of [{P(OMe)3}AgO2CCMe2(OH)] (8b)
91
7.3.24
Synthesis of [{P(OMe)3}AgO2C(C4H3O)] (8c)
92
7.3.25
Synthesis of [{P(OEt)3}AgO2CtBu] (9a)
93
7.3.26
Synthesis of [{P(OEt)3}AgO2CCMe2(OH)] (9b)
93
7.3.27
n
t
Synthesis of [(P Bu3)2AgO2C Bu] (10a)
n
94
7.3.28
Synthesis of [(P Bu3)2AgO2CCH2Ph] (10b)
95
7.3.29
Synthesis of [(PnBu3)2AgO2CCHPh2] (10c)
95
7.3.30
7.3.31
n
96
n
97
n
Synthesis of [(P Bu3)2AgO2CCMe=CHMe] (10d)
Synthesis of [(P Bu3)2AgO2C(CH2)10CH3] (10e)
7.3.32
Synthesis of [(P Bu3)2AgO2C(C4H3O)] (10f)
98
7.3.33
Synthesis of [(PnBu3)2AgO2CCH=CH(C4H3O)] (10g)
99
7.3.34
7.3.35
n
Synthesis of [(P Bu3)2AgO2CC(O)CH3] (10h)
n
Synthesis of [(P Bu3)2AgO2CC(O)CH2CH3] (10i)
t
100
101
7.3.36
Synthesis of [{P(OMe)3}2AgO2C Bu] (11a)
101
7.3.37
Synthesis of [{P(OMe)3}2AgO2CCMe2(OH)] (11b)
102
Experimental Section
78
7.3.38
Synthesis of [{P(OMe)3}2AgO2C(C4H3O)] (11c)
103
7.3.39
Synthesis of [{P(OEt)3}2AgO2CtBu] (12a)
104
7.3.40
Synthesis of [{P(OEt)3}2AgO2CCMe2(OH)] (12b)
104
7.3.41
n
t
Synthesis of [(P Bu3)3AgO2C Bu] (13a)
105
n
7.3.42
Synthesis of [(P Bu3)3AgO2C(CH2)10CH3] (13b)
106
7.3.43
Synthesis of [(PnBu3)3AgO2C(C4H3O)] (13c)
106
7.3.44
7.3.45
n
107
n
108
n
Synthesis of [(P Bu3)3AgO2CCH=CH(C4H3O)] (13d)
Synthesis of [(P Bu3)3AgO2CC(O)CH3] (13e)
7.3.46
Synthesis of [(P Bu3)3AgO2CC(O)CH2CH3] (13f)
109
7.3.47
Synthesis of [{P(OMe)3}3AgO2CtBu] (14a)
110
7.3.48
Synthesis of [{P(OMe)3}3AgO2CCMe2(OH)] (14b)
110
t
7.3.49
Synthesis of [{P(OEt)3}3AgO2C Bu] (15a)
111
7.3.50
Synthesis of [{P(OEt)3}3AgO2CCMe2(OH)] (15b)
112
7.3.51
Synthesis of [(PnBu3)2AgO2CCH2CO2Ag(PnBu3)2] (16a)
112
7.3.52
7.3.53
n
n
Synthesis of [(P Bu3)3AgO2CCH2CO2Ag(P Bu3)3] (16b)
113
n
n
114
n
n
Synthesis of [(P Bu3)2AgO2CCH2CH2CO2Ag(P Bu3)2] (16c)
7.3.54
Synthesis of [(P Bu3)3AgO2CCH2CH2CO2Ag(P Bu3)3] (16d)
114
7.3.55
Synthesis of [(PnBu3)AgO2C(C4H3S)CO2Ag(PnBu3)] (16e)
115
n
n
7.3.56
Synthesis of [(P Bu3)2AgO2C(C4H3S)CO2Ag(P Bu3)2] (16f)
116
7.3.57
Synthesis of [HO-2-(C6H4)C(H)N(C6H4)-4-OMe] (19a)
117
7.3.58
Synthesis of [HO-2-(C6H4)C(H)N(C6H4)-4-Me] (19b)
117
7.3.59
Synthesis of [Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}] (20a)
118
7.3.60
Synthesis of [Ag{O-2-(C6H4)C(H)N(C6H4)-4-Me}] (20b)
119
7.3.61
7.3.62
7.3.63
7.3.64
n
119
n
120
n
121
n
122
Synthesis of [(P Bu3)Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}] (21a)
Synthesis of [(P Bu3)Ag{O-2-(C6H4)C(H)N(C6H4)-4-Me}] (21b)
Synthesis of [(P Bu3)2Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}] (21c)
Synthesis of [(P Bu3)2Ag{O-2-(C6H4)C(H)N(C6H4)-4-Me}] (21d)
79
Experimental Section
7.3.1 Synthesis of [AgO2CtBu] (3a)
Silver nitrate (8.49 g, 50 mmol) dissolved in a mixture of
30 mL of ethanol and 2 mL of acetonitrile was added to pivalic
acid (5.10 g, 50 mmol) dissolved in 30 mL of ethanol at 25 °C.
After
stirring
the
mixture
for
5
min,
a
solution
of
triethylamine (5.05 g, 50 mmol) dissolved in 5 mL of ethanol
was added dropwise. The reaction mixture was stirred for 2 h.
The white precipitate obtained was filtered, off washed three
times with 5 mL of ethanol and dried in oil-pump vacuum.
Yield: 9.58 g (45.83 mmol, 91 % based on pivalic acid).
Mp: 135 °C (decomp.). Elemental analysis: calcd. for C5H9O2Ag
(208.99) C, 28.74; H, 4.34 %. Found: C, 28.75; H, 4.20 %. IR
(KBr) [cm-1]: [νCO2,as] 1543 (vs), [νCO2,s] 1411 (vs).
DMSO): δ = 1.08 (s, 9 H).
13
1
H NMR (d6-
C{1H} NMR (d6-DMSO): δ = 16.40 (C3),
29.7 (C2), 182.7 (C1).
[(C3H3)3C2C1OOAg]
7.3.2 Synthesis of [AgO2CCMe2(OH)] (3b)
Complex 3b can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted with 2-hydroxyisobutyric acid (5.20 g, 50 mmol) and
triethylamine
(5.05
g,
50
mmol).
After
appropiate
work-up,
complex 3b was obtained as a white solid.
Yield: 8.81 g (41.77 mmol, 83 % based on 2-hydroxyisobutyric
acid).
Mp: 150 °C (decomp.). Elemental analysis: calcd. for C4H7O3Ag
(210.97) C, 22.77; H, 3.34 %. Found: C, 22.45; H, 3.38 %. IR
(KBr) [cm-1]: [νOH] 3486 (s), [νCO2,as] 1564 (s), [νCO2,s] 1409
(vs).
OH).
1
13
H NMR (d6-DMSO): δ = 1.22 (s, 6 H, CH3), 4.31 (s, 1 H,
C{1H} NMR (d6-DMSO): δ = 29.5 (C2), 73.0 (C3), 181.4 (C1).
[HOC3(C2H3)2C1OOAg]
80
Experimental Section
7.3.3 Synthesis of [AgO2CCH2Ph] (3c)
Complex 3c can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted
with
phenyl
acetic
acid
(6.80g,
50
mmol)
and
triethylamine (5.05 g, 50 mmol). After appropriate work-up,
complex 3c was obtained as a white solid.
Yield: 9.98 g (41.07 mmol, 82 % based on phenyl acetic acid).
Mp: 120 °C (decomp.). Elemental analysis: calcd. for C8H7O2Ag
(243.01) C, 39.54; H, 2.90 %. Found: C, 39.26; H, 3.14 %. IR
(KBr)
[cm-1]:
[νCO2,as]
1568
(vs),
[νCO2,s]
1383
(vs).
1
H
NMR
(DMSO): δ = 3.44 (s, 2 H, CH2), 7.19 – 7.25 (m, 5 H, Ph).
7.3.4 Synthesis of [AgO2CCHPh2] (3d)
Complex 3d can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted
with
diphenyl
acetic
acid
(10.61
g,
50
mmol)
and
triethylamine (5.05 g, 50 mmol). After appropriate work-up,
complex 3d was obtained as a white solid, which is not soluble
in organic solvents.
Yield: 14.60 g (45.76 mmol, 91 % based on diphenyl acetic
acid).
Mp: 100 °C (decomp.). Elemental analysis: calcd. for C14H11O2Ag
(319.11) C, 52.69; H, 3.47 %. Found: C, 52.61; H, 3.86 %. IR
(KBr) [cm-1]: [νCO2,as] 1598 (vs), [νCO2,s] 1365 (vs).
7.3.5 Synthesis of [AgO2CCMe=CHMe] (3e)
Complex 3e can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted with tiglic acid (5.00 g, 50 mmol) and triethylamine
(5.05 g, 50 mmol). After appropriate work-up, complex 3e was
obtained as a white solid, which is not soluble in organic
solvents.
Yield: 9.01 g (43.55 mmol, 87 % based on tiglic acid).
81
Experimental Section
Mp: 162 °C (decomp.). Elemental analysis: calcd. for C5H7O2Ag
(206.98) C, 29.02; H, 3.41 %. Found: C, 28.71; H, 3.36 %. IR
(KBr) [cm-1]: [νC=C] 1654 (m), [νCO2,as] 1552 (vs), [νCO2,s] 1393
(vs).
7.3.6 Synthesis of [AgO2C(CH2)10CH3] (3f)
Complex 3f can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted
with
dodecanoic
acid
(10.01
g,
50
mmol)
and
triethylamine (5.05 g, 50 mmol). After appropriate work-up,
complex 3f was obtained as a white solid, which is not soluble
in organic solvents.
Yield: 12.98 g (42.26 mmol, 85 % based on dodecanoic acid).
Mp: 180 °C (decomp.). Elemental analysis: Calcd. for C12H23O2Ag
(307.18) C, 46.92; H, 7.55 %. Found: C, 46.80; H, 7.50 %. IR
(KBr) [cm-1]: [νCO2,as] 1561 (vs), [νCO2,s] 1419 (vs).
7.3.7 Synthesis of [AgO2C(C4H3O)] (3g)
Complex 3g can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted with furan-2 carboxylic acid (5.60 g, 50 mmol) and
triethylamine
(5.05
g,
50
mmol).
After
appropiate
work-up,
complex 3g was obtained as a white solid, which is not soluble
in organic solvents.
Yield: 9.81 g (44.82 mmol, 89 % based on furan-2 carboxylic
acid).
Mp: 182 °C (decomp.). Elemental analysis: calcd. for C5H3O3Ag
(218.95) C, 27.43; H, 1.38 %. Found: C, 27.62; H, 1.58 %. IR
(KBr) [cm-1]: [νC=C] 1694 (w), [νCO2,as] 1604 (vs), [νCO2,s] 1402
(vs).
82
Experimental Section
7.3.8 Synthesis of [AgO2CCH=CH(C4H3O)] (3h)
Complex 3h can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted
with
furylacrylic
acid
(6.90
g,
50
mmol)
and
triethylamine (5.05 g, 50 mmol). After appropriate work-up,
complex 3h was obtained as a white solid, which is not soluble
in organic solvents.
Yield: 11.42 g (46.62 mmol, 93 % based on furylacrylic acid).
Mp: 126 °C (decomp.). Elemental analysis: calcd. for C7H5O3Ag
(244.98) C, 34.32; H, 2.06 %. Found: C, 34.74; H, 1.84 %. IR
(KBr) [cm-1]: [νC=C] 1686 (s) [νCO2,as] 1550 (m), [νCO2,s] 1384
(vs).
7.3.9 Synthesis of [AgO2CC(O)CH3] (3i)
Complex 3i can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (4.24 g, 25 mmol) was
reacted with pyruvic acid (2.20 g, 25 mmol) and triethylamine
(2.52 g, 25 mmol). After appropriate work-up, complex 3i was
obtained as a white solid which is not soluble in organic
solvents.
Yield: 4.22 g (21.68 mmol, 86 % based on pyruvic acid).
Mp: 134 °C (decomp.). Elemental analysis: calcd. for C3H3O3Ag
(194.92) C, 18.49; H, 1.55 %. Found: C, 18.03; H, 1.82 %. IR
(KBr) [cm-1]: [νC=O] 1712 (vs) [νCO2,as] 1633 (m), [νCO2,s] 1393
(vs).
7.3.10 Synthesis of [AgO2CC(O)CH2CH3] (3j)
Complex 3j can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (4.24 g, 25 mmol) was
reacted
with
2-ketobutyric
acid
(2.55
g,
25
mmol)
and
triethylamine (2.52 g, 25 mmol). After appropriate work-up,
complex 3j was obtained as a white solid, which is not soluble
in organic solvents.
Experimental Section
83
Yield: 4.21 g (20.19 mmol, 80 % based on 2-ketobutyric acid).
Mp: 139 °C (decomp.). Elemental analysis: calcd. for C4H5O3Ag
(208.95) C, 22.99; H, 2.41 %. Found: C, 23.68; H, 2.80 %. IR
(KBr) [cm-1]: [νC=O] 1715 (vs) [νCO2,as] 1633 (vs), [νCO2,s] 1386
(vs).
7.3.11 Synthesis of [AgO2CCH2CO2Ag] (3k)
Complex 3k can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted with malonic acid (2.60 g, 25 mmol) and triethylamine
(5.05 g, 50 mmol). After appropriate work-up, complex 3k was
obtained as a white solid, which is not soluble in organic
solvents.
Yield: 6.49 g (20.42 mmol, 81 % based on malonic acid ).
Mp: 166 °C (decomp.). Elemental analysis: Calcd. for C3H2O4Ag2
(317.78) C, 11.34; H, 0.63 %. Found: C, 11.69; H, 0.91 %. IR
(KBr) [cm-1]: [νCO2,as] 1564 (vs), [νCO2,s] 1399 (s).
7.3.12 Synthesis of [AgO2CCH2CH2CO2Ag] (3l)
Complex 3l can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (8.49 g, 50 mmol) was
reacted with succinic acid (2.95 g, 25 mmol) and triethylamin
(5.05 g, 50 mmol). After appropriate work-up, complex 3l was
obtained as a white solid, which is not soluble in organic
solvents.
Yield: 7.07 g (21.33 mmol, 85 % based on succinic acid ).
Mp: 101 °C (decomp.). Elemental analysis: calcd. for C4H4O4Ag2
(331.81) C, 14.48; H, 1.22 %. Found: C, 15.09; H, 1.61 %. IR
(KBr) [cm-1]: [νCO2,as] 1569 (vs), [νCO2,s] 1397 (s).
84
Experimental Section
7.3.13 Synthesis of [AgO2C(C4H2S)CO2Ag] (3m)
Complex 3m can be synthesized as described in Section 7.
3.1. In this respect, silver nitrate (6.79 g, 40 mmol) was
reacted with thiophene-2,5 dicarboxylic acid (3.44 g, 20 mmol)
and triethylamine (4.04 g, 40 mmol). After appropriate workup, complex 3m was obtained as a white solid which is not
soluble in organic solvents.
Yield:
6.41
g
(16.62
mmol,
83
%
based
on
thiophene-2,5
dicarboxylic acid ).
Mp: 162 °C (decomp.). Elemental analysis: Calcd. for C6H2O4SAg2
(385.88) C, 19.68; H, 0.52; S, 8.31 %. Found: C, 19.96; H,
0.65; S, 9.04 %. IR (KBr) [cm-1]: [νC=C] 1683 (m), [νCO2,as] 1570
(vs), [νCO2,s] 1383 (s).
7.3.14 Synthesis of [(PnBu3)AgO2CtBu] (7a)
Tri-n-butylphosphan (1.01 g, 5.0 mmol) dissolved in 20 mL
of Et2O was added dropwise to silver(I) pivalate (1.04 g, 5.0
mmol) suspended in 30 mL of Et2O at 25 °C. The reaction mixture
was
stirred
filtered
for
4
through
a
h.
Afterwards
pad
of
the
Celite.
reaction
Removal
mixture
of
is
volatile
materials in oil-pump vacuum produces a brown solid.
Yield: 1.89 g (4.60 mmol, 92 % based on silver(I) pivalate).
Mp: 69 °C. Elemental analysis: calcd. for C17H36O2AgP (411.31)
C, 49.64; H,8.82 %. Found: C, 49.58; H, 8.94 %. IR (KBr) [cm1
]: [νCO2,as] 1545 (vs), [νCO2,s] 1412 (s).
0.88 (t,
3
1
H NMR (CDCl3): δ =
JHH = 5.0 Hz, 9 H, H-4), 1.20 (s, 9 H, H-7), 1.39 –
1.62 (m, 18 H, H-1/H-2/H-3).
(C4), 24.64 (d,
2
C ), 28.12 (d,
187.70 (C5).
31
3
13
C{1H} NMR (CDCl3): δ = 13.97
JCP = 14.90 Hz, C3), 25.38 (d,
2
1
7
1
JCP = 22.01 Hz,
JCP = 3.71 Hz, C ), 28.97 (C ), 39.75 (C6),
P{1H} NMR (CDCl3): δ = –0.4. TG: one step; Tbegin =
152 °C, Tend = 400 °C, ∆m = 72.43 %. DSC: Peak 1: T = 72.21 °C,
∆H1 = 4.30 J/g; Peak 2: T = 303.24 °C, ∆H2 = -12.29 J/g.
85
Experimental Section
O
(C7H3)3C6
P(C1H2C2H2C3H2C4H3)3
Ag
C5
O
7.3.15 Synthesis of [(PnBu3)AgO2CCH2Ph] (7b)
Tri-n-butylphosphan (1.01 g, 5.0 mmol) dissolved in 20 mL
of THF was added dropwise to silver(I) phenyl acetate (1.21 g,
5.0 mmol) suspended in 30 mL of THF at 25 °C. The reaction
mixture was stirred for 4 h. Afterwards the reaction mixture
was filtered through a pad of Celite. Removal of all volatiles
in oil-pump vacuum produces a brown oil.
Yield:
2.09
g
(4.71
mmol,
94
%
based
on
silver(I)
phenyl
acetate).
Elemental analysis: calcd. for C20H34O2AgP (445.33) C, 53.94; H,
7.70 %. Found: C, 53.16; H, 8.01 %. IR (NaCl) [cm-1]: [νCO2,as]
1
1563 (s), [νCO2,s] 1380 (s).
H NMR (CDCl3): δ = 0.86 (t,
3
JHH =
7.10 Hz, 9 H, H-4), 0.88 – 1.46 (m, 18 H, H-1/H-2/H-3), 3.56
(s, 2 H, H-6), 7.13 – 7.29 (m, 5 H, H-Ph).
δ = 13.98 (C4), 24.56 (d,
2
21.64 Hz, C ), 28.15 (d,
(C10),
31
128.67
(C9),
3
1
13
C{1H} NMR (CDCl3):
JCP = 14.70 Hz, C3), 25.27 (d,
1
2
JCP =
6
JCP = 3.83 Hz, C ), 43.52 (C ) 126.52
(C8),
129.66
137.60
(C7),
179.09
(C5).
P{1H} NMR (CDCl3): δ = 0.5. TG: one step; Tbegin = 170 °C, Tend
= 312 °C, ∆m = 79.27 %. DSC: Peak 1: T = 93.55 °C, ∆H1 = 2.98
J/g; Peak 2: T = 245.99 °C, ∆H2 = 19.83 J/g; Peak 3: T = 265.98
°C, ∆H3 = -5.90 J/g.
C9
C8
C10
C9
O
C7
C8
Ag
C6 H2C5
O
P(C1H2C2H2C3H2C4H3)3
86
Experimental Section
7.3.16. Synthesis of [(PnBu3)AgO2CCHPh2] (7c)
Complex 7c can be synthesized as described in Section
7.1.15.
In
this
respect,
tri-n-butylphosphan
(1.01
g,
5.0
mmol) was reacted with silver(I) diphenyl acetate (1.59 g, 5.0
mmol). After appropriate work-up, complex 7c was obtained as a
brown oil.
Yield: 2.54 g (4.87 mmol, 97 % based on silver(I) diphenyl
acetate).
Elemental analysis: calcd. for C26H38O2AgP (521.433) C, 59.89;
H,
7.35
%.
Found:
C,
59.44;
H,
7.63
[νCO2,as] 1566 (vs), [νCO2,s] 1358 (vs).
(t,
3
1
%.
IR
(NaCl)
H NMR (CDCl3): δ = 0.85
JHH = 7.10 Hz, 9 H, H-4), 1.33 – 1.54 (m, 18 H, H-1/H-2/H-
3), 5.03 (s, 1H, H-6), 7.09 – 7.34 (m, 10 H, H-Ph).
(CDCl3): δ = 14.04 (C4), 24.55 (d,
(d,
2
(C6),
[cm-1]:
JCP = 20.46 Hz, C2), 28.06 (d,
(C10),
126.77
178.81 (C5).
31
128.59
(C8),
3
13
C{1H} NMR
JCP = 14.33 Hz, C3), 25.12
1
JCP = 3.47 Hz, C1), 59.78
129.20
(C9),
141.56
(C7),
P{1H} NMR (CDCl3): δ = -1.6. TG: three steps; 1:
Tbegin = 100 °C, Tend = 202 °C, ∆m = 8.59 %; 2: Tbegin = 202 °C,
Tend = 242 °C, ∆m = 31.72 %; 3: Tbegin = 202 °C, Tend = 349, ∆m =
39.60 %. DSC: Peak 1 = 84.40 °C, ∆H1 = 3.04 J/g; Peak 2 =
202.30 °C, ∆H2 = -13.08 J/g; Peak 3 = 272.85 °C, ∆H3 = -33.48
J/g.
C10
C9
C9
C8
C8
C7
O
Ag
C6HC5
C8
O
C7
C9
C8
C10
C9
P(C1H2C2H2C3H2C4H3)3
87
Experimental Section
7.3.17 Synthesis of [(PnBu3)AgO2CCMe=CHMe (7d)
Complex 7d can be synthesized as described in Section
7.3.15.
In
this
respect,
tri-n-butylphosphan
(1.01
g,
5.0
mmol) was reacted with silver(I) tiglate (1.03 g, 5 mmol).
After appropriate work-up, complex 7d was obtained as a brown
oil.
Yield: 1.95 g (4.77 mmol, 95 % based on silver(I) tiglate).
Elemental analysis: calcd. for C17H34O2AgP (409.30) c,49.89; H,
8.37 %. Found: C, 49.55; H, 8.47 %. IR (NaCl) [cm-1]: [νC=C]
1
1656 (m), [νCO2,as] 1554 (vs), [νCO2,s] 1388 (vs).
δ = 0.87 (t,
H NMR (CDCl3):
3
JHH = 7.02 Hz, 9 H, H-4), 1.30 – 1.65 (m, 18 H,
H-1/H-2/H-3), 1.69 (d,
3
JHH = 7.03 Hz, 3 H, H-9), 2.08 (bs, 3
H, H-7), 6.67 – 6.75 (m, 1 H, H-8).
13
C{1H} NMR (CDCl3): δ =
13.32 (C9), 13.64 (C4), 14.19 (C7), 24.23 (d,
C3), 25.46 (d,
3
JCP = 14.76 Hz,
2
JCP = 21.80 Hz, C2), 27.91 (C1), 132.16 (C6),
132.29 (C8), 176.38 (C5).
31
P{1H} NMR (CDCl3): δ = 0.6. TG: one
step; Tbegin = 123 °C, Tend = 358 °C, ∆m = 70.44 %. DSC: Peak 1:
T = 112 °C, ∆H1 = 0.96 J/g, Peak 2: T = 240 °C, ∆H2 = -24.11
J/g, Peak 3: T = 246 °C, ∆H3 = 16.34 J/g, Peak 4: T = 383 °C,
∆H4 = -12.85 J/g.
O
H
C5
C8
H3 C9
C6
Ag
O
C7 H3
P(C1H2C2H2C3H2C4H3)3
88
Experimental Section
7.3.18 Synthesis of [(PnBu3)AgO2C(CH2)10CH3] (7e)
Complex 7e can be synthesized as described in Section
7.3.15.
mmol)
In
was
this
respect,
reacted
with
tri-n-butylphosphan
silver(I)
dodecanoate
(1.01
g,
5.0
(1.53
g,
5.0
mmol). After appropriate work-up, complex 7e was obtained as a
brown oil.
Yield:
2.50
g
(4.92
mmol,
98
%
based
on
silver(I)
dodecanoate).
Elemental analysis: calcd. for C24H50O2AgP (509.50) C, 56.58; H,
9.89 %. Found: C, 56.23; H, 10.02 %. IR (NaCl) [cm-1]: [νCO2,as]
1559 (vs), [νCO2,s] 1387 (vs).
1
H NMR (CDCl3): δ = 0.76 – 0.94
(m, 12 H, H-4/H-8), 1.16 – 1.59 (m, 36 H, H-1/H-2/H-3/H-7),
3
2.24 (t,
JHH = 7.32 Hz, 2H, H-6).
13
C{1H} NMR (CDCl3): δ = 13.68
(C4), 14.18 (C8), 22.75 (C7), 24.29 (d,
25.12 (d,
3
JCP = 14.63 Hz, C3),
2
JCP = 21.61 Hz, C2), 26.72 (C7), 27.94 (d,
1
JCP = 3.64
Hz, C1), 29.41 (C7), 29.61 (C7), 29.65 (C7), 29.71 (C7), 29.75
(C7), 31.98 (C7), 36.22 (C6), 182.33 (C5).
= -1.2 (d,
31
P{1H} NMR (CDCl3): δ
J107/109Ag31P = 903.38 Hz). DSC: Peak 1: T = 81 °C, ∆H1
1
= 0.50 J/g; Peak 2: T = 264 °C, ∆H2 = 40.29 J/g).
O
C8H3(C7H2)9C6H2
C5
Ag
P(C1H2C2H2C3H2C4H3)3
O
7.3.19 Synthesis of [(PnBu3)AgO2C(C4H3O)] (7f)
Complex 7f can be synthesized as described in Section
7.3.15.
In
this
respect,
tri-n-butylphosphan
(1.01
g,
5.0
mmol) was reacted with furan-2 silver(I) carboxylate (1.09 g,
5.0 mmol). After appropriate work-up, complex 7f was obtained
as a brown solid.
Yield: 1.97 g (4.68 mmol, 93 % based on furan-2 silver(I)
carboxylate).
89
Experimental Section
Mp: 67 °C. Elemental analysis: calcd. for C17H30O3AgP (421.27)
C, 48.47; H, 7.18 %. Found: C, 48.23; H, 7.16 %. IR (KBr) [cm1
]: [νC=C] 1620 (m), [νCO2,as] 1605 (vs), [νCO2,s] 1409 (vs).
3
(CDCl3): δ = 0.90 (t,
3
7.44 (dd,
3
3
JHH = 3.34 Hz,
2
4
JHH = 3.34 Hz,
4
JHH = 1.75 Hz,
3
JHH = 1.75 Hz, 1
JHH = 0.76 Hz,1 H, H-7),
JHH = 0.76 Hz,1 H, H-9).
(CDCl3): δ = 13.75 (C4), 24.33 (d,
(d,
H NMR
JHH = 7.10 Hz, 9 H, H-4), 1.37 – 1.81 (m,
18 H, H-1/H-2/H-3), 6.40 (dd,
H, H-8), 7.00 (dd,
1
3
JCP = 22.38 Hz, C2), 28.08 (d,
13
C{1H} NMR
JCP = 14.74 Hz, C3), 25.15
1
JCP = 3.77 Hz, C1), 111.34
(C8), 114.84 (C7), 144.20 (C6), 149.78 (C9), 166.43 (C5).
NMR (CDCl3): δ = 0.4 (d,
1
31
P{1H}
J107/109Ag31P = 715.11 Hz). DSC: Peak 1:
T = 73 °C, ∆H1 = 14.18 J/g; Peak 2: T = 224 °C, ∆H2 = 23.64
J/g.
O
O
H
C9
C8
C6
P(C1H2C2H2C3H2C4H3)3
Ag
C5
O
C7
H
H
7.3.20 Synthesis of [(PnBu3)AgO2CC(O)CH3] (7g)
Complex 7g can be synthesized as described in Section
7.3.15.
In
this
tri-n-butylphosphan
respect,
(1.01
g,
5.0
mmol) was reacted with silver(I) pyruvate (0.97 g, 5.0 mmol).
After approppriate work-up, complex 7g was obtained as a brown
oil.
Yield:
1.92
g
(4.84
mmol,
96
%
based
on
silver(I)
pyruvate).
Elemental analysis: calcd. for C15H30O3AgP (397.24) C, 45.35; H,
7.61 %. Found: C, 45.89; H, 7.43 %. IR (NaCl) [cm-1]: [νCO] 1707
(vs) [νCO2,as] 1621 (vs), [νCO2,s] 1412 (vs).
0.73 (t,
3
1
H NMR (CDCl3): δ =
JHH = 7.02 Hz, 9 H, H-4), 1.15 – 1.51 (m, 18 H, H-
1/H-2/H-3), 2.24 (s, 3 H ,H-7).
(C7), 13.64 (C4), 24.17 (d,
2
3
= 20.82 Hz), C ), 27.84 (d,
13
C{1H} NMR (CDCl3): δ = 8.61
JCP = 14.37 Hz, C3), 24.87 (d,
1
1
2
JCP
5
JCP = 3.74 Hz, C ), 168.28 (C ),
90
Experimental Section
201.42 (C6).
31
P{1H} NMR (CDCl3): δ = -1.1. TG: three steps; 1:
Tbegin = 100 °C, Tend = 174 °C, ∆m = 10.31 %; 2: Tbegin = 174 °C,
Tend = 243 °C, ∆m = 51.22 %; 3: Tbegin = 243 °C, Tend = 402, ∆m =
9.81 %. DSC: Peak 1: T = 99 °C, ∆H1 = 8.31 J/g; Peak 2: T = 225
°C, ∆H2 = -18.83 J/g; Peak 3: T = 264 °C, ∆H3 = 2.14 J/g.
O
C7H3
O
C6
P(C1H2C2H2C3H2C4H3)3
Ag
C5
O
7.3.21 Synthesis of [(PnBu3)AgO2CC(O)CH2CH3] (7h)
Complex 7h can be synthesized as described in Section
7.3.15.
In
this
tri-n-butylphosphan
respect,
(1.01
g,
5.0
mmol) was reacted with silver(I) 2-ketobutyrate (1.04 g, 5.0
mmol). After appropriate work-up, complex 7h was obtained as a
brown oil.
Yield:
2.02
g
(4.93
mmol,
98
%
based
on
silver(I)
2-
ketobutyrate).
Elemental analysis: calcd. for C16H32O3AgP (411.27) C, 46.73; H,
7.84 %. Found: C, 46.38; H, 8.09 %. IR (NaCl) [cm-1]: [νCO] 1709
(vs) [νCO2,as] 1613 (vs), [νCO2,s] 1380 (s).
0.88 (t,
3
1
H NMR (CDCl3): δ =
JHH = 7.04 Hz, 9 H, H-4), 1.00 (t,
3
JHH = 7.27 Hz, 3
H, H-8), 1.25 – 1.61 (m, 18 H, H-1/H-2/H-3), 2.78 (q,
7.30 Hz, 2 H, H-7).
13
= 22.15 Hz, C2), 27.98 (d,
31
JHH =
C{1H} NMR (CDCl3): δ = 7.47 (C8), 8.66
(C7), 13.70 (C4), 24.25 (d,
(C6).
3
3
1
JCP = 14.65 Hz, C3), 25.00 (d,
2
JCP
JCP = 3.77 Hz, C1), 168.94 (C5), 203
P{1H} NMR (CDCl3): δ = -0.0. TG: one step; Tbegin = 104
°C, Tend = 398 °C, ∆m = 71.61 %. DSC: Peak 1: T = 54 °C, ∆H1 =
19.48 J/g; Peak 2: T = 103 °C, ∆H2 = -11.59 J/g; Peak 3: T =
124 °C, ∆H3 = -4.81 J/g).
91
Experimental Section
O
8
7
C H3C H2
O
C6
P(C1H2C2H2C3H2C4H3)3
Ag
C5
O
7.3.22 Synthesis of [{P(OMe)3}AgO2CtBu] (8a)
Complex 8a can be synthesized as described in Section
7.3.14. in this respect, trimethylphosphite (0.62 g, 5 mmol)
was reacted with silver(I) pivalate (1.04 g, 5 mmol). After
appropiate work-up, complex 8a was obtained as a brown oil.
Yield: 1.51 g (4.53 mmol, 90 % based on silver(I) pivalate).
Elemental analysis: calcd. for C8H18O5AgP (333.06) C, 28.92; H,
5.46 %. Found: C, 28.64; H, 5.54 %. IR (NaCl) [cm-1]: [νCO2,as]
1557 (vs), [νCO2,s] 1402 (s).
H-4), 3.57 (d,
3
1
H NMR (CDCl3): δ = 1.01 (s, 9 H,
JPH = 13.52 Hz, 9 H, H-1).
= 28.89 (C4), 39.55 (C3), 51.94 (d,
(C2).
31
2
13
C{1H} NMR (CDCl3): δ
JCP = 4.40 Hz, C1), 188.17
P{1H} NMR (CDCl3): δ = 128.9. DSC: Peak 1: T = 180 °C,
∆H1 = -22.39 J/g; Peak 2: T = 201 °C, ∆H2 = -9.03 J/g.
O
(C4H3)3C3
P(OC1H3)3
Ag
C2
O
7.3.23 Synthesis of [{P(OMe)3}AgO2CCMe2(OH) (8b)
Complex 8b can be synthesized as described in Section
7.3.14. In this respect, trimethylphosphite (0.62 g, 5.0 mmol)
was reacted with silver(I) 2-hydroxyisobutyrate (1.05 g, 5.0
mmol). After appropiate work-up, complex 8b was obtained as a
brown solid.
Yield:
1.60
g
(4.78
mmol,
95
%
based
on
silver(I)
2-
hydroxyisobutyrate).
Mp: 69 °C decomp. Elemental analysis: calcd. for C7H16O6AgP
(335.03) C, 25.09; H, 4.81 %. Found: C, 24.26; H, 4.40 %. IR
92
Experimental Section
(NaCl) [cm-1]: [νOH] 3413 (s) [νCO2,as] 1581 (vs), [νCO2,s] 1409
(s).
1
13.5 Hz, 9 H, H-1), 4.31 (s, 1 H, OH).
28.60 (C3), 52.20 (d,
(C2).
3
H NMR (CDCl3): δ = 1.43 (s, 6 H, H-3), 3.69 (d,
31
13
JPH =
C{1H} NMR (CDCl3): δ =
2
JCP = 3.64 Hz, C1), 73.24 (C4), 184.42
P{1H} NMR (CDCl3): δ = 126.3. DSC: Peak 1: T = 68 °C,
∆H1 = 66.82 J/g; Peak 2: T = 151 °C, ∆H2 = -151.84 J/g; Peak 3:
T = 170 °C, ∆H3 = -102.35 J/g.
O
HOC4(C3H3)2
Ag
C2
P(OC1H3)3
O
7.3.24 Synthesis of [{P(OMe)3}AgO2C(C4H3O)] (8c)
Complex 8c can be synthesized as described in Section
7.3.14. In this respect, trimethyphosphite (0.62 g, 5.0 mmol)
was reacted with furan-2 silver(I) carboxylate (1.09 g, 5.0
mmol). After appropriate work-up, complex 8c can be obtained
as a brown solid.
Yield: 1.68 g (4.91 mmol, 98 % based on furan-2 silver(I)
carboxylate).
Mp: 45 °C. Elemental analysis: calcd. for C8H12O6AgP (343.02) C,
28.01; H, 3.53 %. Found: C, 28.20; H, 3.34 %. IR (KBr) [cm-1]:
[νC=C] 1627 (m), [νCO2,as] 1607 (vs), [νCO2,s] 1404 (vs).
(CDCl3): δ = 3.64 (d,
3
JHP = 13.5 Hz, 9 H, H-1), 6.38 (dd,
3.31 Hz, 3JHH = 1.74 Hz 1 H, H-5), 6.99 (dd,
= 0.82 Hz, 1 H, H-4), 7.40 (dd,
1 H, H-6).
13
1
3
H NMR
3
JHH =
JHH = 3.31 Hz,
3
JHH = 1.74 Hz,
C{1H} NMR (CDCl3): δ = 51.74 (d,
4
JHH
4
JHH = 0.82 Hz,
2
JCP = 4.77 Hz,
C1), 111.37 (C5), 114.89 (C4), 144.01 (C3), 149.74 (C6), 166.08
(C2).
31
P{1H} NMR (CDCl3): δ = 129.3. DSC: Peak 1: T = 61 °C,
∆H1 = 8.80 J/g; Peak 2: T = 166 °C, ∆H2 = -54.17 J/g; Peak 3: T
= 315 °C, ∆H3 = -23.61 J/g.
93
Experimental Section
O
O
H
C6
C3
C5
P(OC1H3)3
Ag
C2
O
C4
H
H
7.3.25 Synthesis of [{P(OEt)3}AgO2CtBu] (9a)
Complex 9a can be synthesized as described in Section
7.3.14. In this respect, triethylphosphite (0.83g, 5.0 mmol)
was reacted with silver(I) pivalate (1.04 g, 5.0 mmol). After
appropriate work-up, complex 9a was obtained as a brown oil.
Yield: 1.84 g (4.90 mmol, 98 % based on silver(I) pivalate).
Elemental analysis: calcd. for C11H24O5AgP (375.12 ) C, 35.29;
H,
6.47
%.
Found:
C,
34.99;
H,
6.62
[νCO2,as] 1544 (vs), [νCO2,s] 1403 (vs).
(s, 9 H, H-5), 1.09 (t,
13
(m, 6 H, H-1).
1
%.
IR
(NaCl)
[cm-1]:
H NMR (CDCl3): δ = 0.99
3
JHH = 7.11 Hz, 9 H, H-2), 3.77 – 3.89
C{1H} NMR (CDCl3): δ = 16.32 (d,
3
JPC = 6.5 Hz,
C2), 28.59 (C5), 39.14 (C4), 60.76 (C1), 186.49 (C3).
31
P{1H} NMR
(CDCl3): δ = 123.9. DSC: Peak 1: T = 192 °C, ∆H1 = -14.54 J/g;
Peak 2: T = 217 °C, ∆H2 = 5.95 J/g.
O
(C5H3)3C4
P(OC1H2C2H3)3
Ag
C3
O
7.3.26 Synthesis of [{P(OEt)3}AgO2CCMe2(OH)] (9b)
Complex 9b can be synthesized as described in Section
7.3.14. In this respect, triethylphosphite (0.83 g, 5.0 mmol)
was
reacted
with
silver(I)
2-hydroxyisobutyrate
(1.05
g,
5mmol). After appropriate work-up, complex 9b was obtained as
a brown oil.
Yield:
1.82
g
(4.84
mmol,
hydroxyisobutyrate).
96
%
based
on
silver(I)
2-
94
Experimental Section
Elemental analysis: calcd. for C10H22O6AgP (377.12) C, 31.85; H,
5.88 %. Found: C, 31.66; H, 5.62 %. IR (NaCl) [cm-1]: [νOH]
3432(s) [νCO2,as] 1581 (s), [νCO2,s] 1391 (s).
1.34 (t,
1
H NMR (CDCl3): δ =
3
JHH = 7.50 Hz, 9 H, H-2), 1.46 (s, 6 H, H-4), 3.26
(s, 1 H, OH), 4.02 – 4.17 (m, 6 H, H-1).
= 16.69 (d,
13
C{1H} NMR (CDCl3): δ
3
JPC = 6.79 Hz, C2), 28.54 (C4), 61.92 (d,
4.33 Hz, C1), 73.13 (C5), 185.07 (C3).
31
2
JPC =
P{1H} NMR (CDCl3): δ =
121.2. DSC: Peak 1: T = 167 °C, ∆H1 = -5.52 J/g; Peak 2: T =
176 °C, ∆H2 = -20.24 J/g, Peak 3: T = 305 °C, ∆H3 = 4.15 J/g.
O
5
Ag
C3
4
HOC (C H3)2
P(OC1H2C2H3)3
O
7.3.27 Synthesis of [(PnBu3)2AgO2CtBu] (10a)
Complex 10a can be synthesized as described in Section
7.3.14. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was reacted with silver(I) pivalate (1.04 g, 5.0 mmol). After
appropriate work-up, complex 10a was obtained as a brown oil.
Yield: 2.96 g (4.83 mmol, 96 % based on silver(I) pivalate).
Elemental analysis: calcd. for C29H63O2AgP2 (613.63) C, 56.76;
H, 10.35 %. Found: C, 56.92; H, 10.07 %. IR (NaCl) [cm-1]:
[νCO2,as] 1558 (vs), [νCO2,s] 1399 (vs).
(t,
1
H NMR (CDCl3): δ = 0.29
3
JHH = 7.50 Hz, 18 H, H-4), 0.56 (s, 9 H, H-7), 0.74 – 0.95
(m, 36 H, H-1/H-2/H-3).
13
C{1H} NMR (CDCl3): δ = 13.50 (C4),
24.20 (C3), 25.32 (C2), 27.30 (C1), 28.66 (C7), 39.18 (C6),
183.72 (C5).
31
P{1H} NMR (CDCl3): δ = -8.1. TG: one step; Tbegin =
139 °C, Tend = 398 °C, ∆m = 81.17 %. DSC: Peak 1: T = 204 °C,
∆H1 = 1.97 J/g; Peak 2: T = 279 °C, ∆H2 = -7.97 J/g.
P(C1H2C2H2C3H2C4H3)3
O
(C7H3)3C6
Ag
C5
O
P(C1H2C2H2C3H2C4H3)3
95
Experimental Section
7.3.28 Synthesis of [(PnBu3)2AgO2CCH2Ph] (10b)
Complex 10b can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was reacted with silver(I) phenyl acetate (1.21 g, 5.0 mmol).
After
appropriate
work-up,
complex
was
10b
obtained
as
a
colourless oil.
Yield:
3.19
g
(4.94
mmol,
98
%
based
on
silver(I)
phenyl
acetate).
Elemental analysis: calcd. for C32H61O2AgP2 (647.65) C, 59.35;
H,
9.49
%.
Found:
C,
59.14;
H,
9.42
[νCO2,as] 1579 (vs), [νCO2,s] 1382 (vs).
(t,
1
%.
IR
(NaCl)
[cm-1]:
H NMR (CDCl3): δ = 0.79
3
JHH = 6.90 Hz, 18 H, H-4), 1.26 – 1.46 (m, 36 H, H-1/H-
2/H-3), 3.45 (s, 2 H, H-6), 6.47 – 7.14 (m, 5 H, H-Ph).
NMR (CDCl3): δ = 14.06 (C4), 24.73 (d,
25.75 (d,
2
JPC = 20.1 Hz, C2), 27.81 (d,
13
C{1H}
3
JPC = 13.2 Hz, C3),
1
JPC = 5.0 Hz, C1),
45.39 (C6), 125.61 (C10), 128.12 (C9), 129.66 (C8), 139.25 (C7),
173.31 (C5).
31
P{1H} NMR (CDCl3): δ = -8.4. TG: one step; Tbegin =
101 °C, Tend = 376 °C, ∆m = 83.81 %. DSC: Peak 1: T = 245 °C,
∆H1 = 1.23 J/g; Peak 2: T = 255 °C, ∆H2 = 1.30 J/g.
C9
C8
C10
C7
C9
C8
P(C1H2C2H2C3H2C4H3)3
O
Ag
C6H2C5
O
P(C1H2C2H2C3H2C4H3)3
7.3.29 Synthesis of [(PnBu3)2AgO2CCH(Ph)2] (10c)
Complex 10c can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was
reacted
with
silver(I)
diphenyl
acetate
(1.59
g,
5.0
mmol). After appropriate work-up, complex 10c was obtained as
a colourless oil.
Yield: 3.49 g (4.82 mmol, 96 % based on silver(I) diphenyl
acetate).
96
Experimental Section
Elemental analysis: calcd. for C38H65O2AgP2 (723.75) C, 63.06;
H,
9.05
%.
Found:
C,
62.79;
H,
9.57
[νCO2,as] 1583 (vs), [νCO2,s] 1365 (vs).
(t,
1
%.
IR
(NaCl)
[cm-1]:
H NMR (CDCl3): δ = 0.87
3
JHH = 7.02 Hz, 18 H, H-4), 1.33 – 1.54 (m, 36 H, H-1/H-
2/H-3), 5.02 (s, H, H-6), 7.12 – 7.40 (m, 10 H, H-Ph).
NMR (CDCl3): δ = 13.84 (C4), 24.50 (d,
25.14 (d,
2
JPC = 13.1 Hz, C2), 27.57 (d,
13
C{1H}
3
JPC = 13.0 Hz, C3),
1
JPC = 4.5 Hz, C1),
60.22 (C6), 125.89 (C10), 127.85 (C9), 129.07 (C8), 142.17 (C7),
175.87 (C5).
31
P{1H} NMR (CDCl3): δ = -8.25. TG: two steps; 1:
Tbegin = 101 °C, Tend = 201 °C, ∆m = 28.49 %;2:
Tbegin = 201 °C,
Tend = 352 °C, ∆m = 56.71 %. DSC: Peak 1: T = 102 °C, ∆H1 = 1.17
J/g; Peak 2: T = 167 °C, ∆H2 = -5.13 J/g; Peak 3: T = 280 °C,
∆H3 = -34.62 J/g.
C10
C9
C9
C8
C8
C7
Ag
C6HC5
C8
O
C7
C9
P(C1H2C2H2C3H2C4H3)3
O
P(C1H2C2H2C3H2C4H3)3
C8
C10
C9
7.3.30 Synthesis of [(PnBu3)2AgO2CCMe=CHMe] (10d)
Complex 10d can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was reacted with silver(I) tiglate (1.03 g, 5.0 mmol). After
appropriate work-up, complex 10d was obtained as a colourless
oil.
Yield: 2.95 g (4.83 mmol, 96 % based on silver(I) tiglate).
Elemental analysis: calcd. for C29H61O2AgP2 (611.62) C, 56.95;
H, 10.05 %. Found. C, 56.60; H, 10.22 %. IR (NaCl) [cm-1]:
[νC=c] 1658 (m), [νCO2,as] 1551 (vs), [νCO2,s] 1384 (vs).
1
H NMR
97
Experimental Section
(CDCl3): δ = 0.80 (t,
3
JHH = 7.04 Hz, 18 H, H-4), 1.21 – 1.50
(m, 36 H, H-1/H-2/H-3), 1.58 (d,
3
JHH = 6.97 Hz, 3 H, H-9),
1.75 (bs, 3 H, H-7), 6.40 – 6.48 (m, 1 H, H-8).
13
C{1H} NMR
(CDCl3): δ = 13.64 (C9),13.79 (C4), 13.92 (C7), 24.58 (d,
9.87 Hz, C3), 25.48 (d,
3
JPC =
2
JPC = 11.13 Hz, C2), 27.62 (C1), 128.08
(C6), 135.44 (C8), 174.82 (C5).
31
P{1H} NMR (CDCl3): δ = -8.3.
TG: one step; Tbegin = 134 °C, Tend = 379 °C, ∆m = 78.92 %. DSC:
Peak 1: T = 261 °C, ∆H1 = -24.61 J/g; Peak 2: T = 269 °C, ∆H2 =
32.30 J/g.
O
H
C5
C8
C6
Ag
O
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
C7 H3
H3 C 9
7.3.31 Synthesis of [(PnBu3)2AgO2C(CH2)10CH3] (10e)
Complex 10e can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was reacted with silver(I) dodecanoate (1.53 g, 5.0 mmol).
After
appropriate
work-up,
complex
10e
was
obtained
as
a
colourless oil.
Yield:
3.48
g
(4.89
mmol,
97
%
based
on
silver(I)
dodecanoate).
Elemental analysis: calcd. for C36H77O2AgP2 (711.82) C, 60.74;
H, 10.90 %. Found: C, 61.12; H, 10.58 %. IR (NaCl) [cm-1]:
[νCO2,as] 1559 (vs), [νCO2,s] 1384 (vs).
1
H NMR (CDCl3): δ = 0.82 –
0.95 (m, 21 H, H-4/H-8), 1.22 – 1.70 (m, 54 H, H-1/H-2/H-3/H7), 2.17 (t,
3
JHH = 7.32 Hz, 2 H, H-6).
13
C{1H} NMR (CDCl3): δ =
13.63 (C4), 13.99 (C8), 22.59 (C7), 24.32 (C3), 25.24 (C7),
25.52 (C2), 26.89 (C7), 27.50 (C1), 29.37 (C7), 29.51 (C1),
29.87 (C7), 31.85 (C7), 37.68 (C6), 179.24 (C5).
31
P{1H} NMR
(CDCl3): δ = -7.9. TG: one step; Tbegin = 124 °C, Tend = 399 °C,
98
Experimental Section
∆m = 82.96 %. DSC: Peak 1: T = 251 °C, ∆H1 = 10.25 J/g; Peak 2:
T = 268 °C, ∆H2 = 10.32 J/g; Peak 3: T = 329 °C, ∆H3 = 8.22
J/g).
O
C5
C8H3(C7H2)9C6H2
Ag
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
O
7.3.32 Synthesis of [(PnBu3)2AgO2C(C4H3O)] (10f)
Complex 10f can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was
reacted
with
furan-2
silver(I)
carboxylate
(1.09,
5.0
mmol). After appropriate work-up, complex 10f was obtained as
a colourless oil.
Yield: 3.03 g (4.86 mmol, 97 % based on furan-2 silver(I)
carboxylate).
Elemental analysis: Calcd. for C29H57O3AgP2 (623.59) C, 55.86; H,
9.21 %. Found: C, 55.31; H, 9.33 %. IR (NaCl) [cm-1]: [νC=C]
1
1610 (m), [νCO2,as] 1593 (vs), [νCO2,s] 1384 (vs).
δ = 0.85 (t,
3
JHH = 7.11 Hz, 18 H, H-4), 1.21 – 1.60 (m, 36 H,
3
H-1/H-2/H-3), 6.33 (dd,
8), 6.85 (dd,
(dd,
JHH = 3.24 Hz,
3
JHH = 3.24 Hz,
3
JHH = 1.74 Hz,
3
JHH = 1.74 Hz, 1 H, H-
4
JHH = 0.77 Hz, 1 H, H-7), 7.35
4
1
13
JHH = 0.77 Hz, 1 H, H-9).
(CDCl3): δ = 13.54 (C4), 24.22 (C3), 25.27 (d,
2
H NMR (CDCl3):
2
JPC = 22.89 Hz,
C ), 27.47 (C ), 110.38 (C ), 111.74 (C ), 144.20 (C6), 152.33
(C9), 164.34 (C5).
8
C{1H} NMR
31
7
P{1H} NMR (CDCl3): δ = -6.9 (d,
1
J107/109Ag31P =
245 Hz). TG: one step; Tbegin = 100 °C, Tend = 361 °C, ∆m = 80.99
%. DSC: Peak 1: T = 206 °C, ∆H1 = 42.14 J/g; Peak 2: T = 255
°C, ∆H2 = -18.92 J/g.
99
Experimental Section
P(C1H2C2H2C3H2C4H3)3
O
O
H
C9
C8
Ag
C5
C6
P(C1H2C2H2C3H2C4H3)3
O
C7
H
H
7.3.33 Synthesis of [(PnBu3)2AgO2CCH=CH(C4H3O)] (10g)
Complex 10g can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was reacted with silver(I) furylacrylate (1.22 g, 5.0 mmol).
After appropriate work-up, complex 10g was obtained as a brown
oil.
Yield:
3.14
g
(4.84
mmol,
96
%
based
on
silver(I)
furylacrylate).
Elemental analysis: calcd. for C31H59O3AgP2 (649.62) C, 57.32;
H, 9.15 %. Found: C, 57.66; H, 8.89 %. IR (NaCl) [cm-1]: [νC=c]
1694 (s) [νCO2,as] 1554 (vs), [νCO2,s] 1370 (vs).
= 0.89 (t,
JHH = 6.9 Hz, 18 H, H-4), 1.37 – 1.61 (m, 36 H, H3
JHH = 1.8 Hz,
3
3
JHH = 3.3 Hz, 1 H, H-10),
JHH = 3.3 Hz, 1 H, H-9), 6.46 (d,
H-6), 7.33 (d,
3
JHH = 15.3 Hz, 1 H,
3
Hz, 1 H, H-11).
3
H NMR (CDCl3): δ
3
1/H-2/H-3), 6.37 (dd,
6.44 (d,
1
JHH = 15.30 Hz, 1 H, H-7), 7.38 (d,
13
3
JHH = 1.8
4
1
C{ H} NMR (CDCl3): δ = 13.81 (C ), 24.51 (d,
JPC = 13.01 Hz, C3), 25.49 (d,
2
JPC = 18.86 Hz, C2), 27.58 (d,
1
JPC = 4.46 Hz, C1), 111.64 (C9), 111.70 (C10), 122.01 (C6),
127.92 (C7), 143.25 (C11), 152.43 (C8), 170.85 (C5).
31
P{1H} NMR
(CDCl3): δ = -8.66. TG: one step; Tbegin = 101 °C, Tend = 398 °C,
∆m = 86.03 %. DSC: Peak 1: T = 117 °C, ∆H1 = 0.57 J/g, Peak 2:
T = 184 °C, ∆H2 = 0.55 J/g, Peak 3: T = 242 °C, ∆H3 =
J/g.
-25.12
100
Experimental Section
O
O
H
C11
C8
C10
C7H
Ag
C5
C6H
O
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
C9
H
H
7.3.34 Synthesis of [(PnBu3)2AgO2CC(O)CH3] (10h)
Complex 10h can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was reacted with silver(I) pyruvate (0.97 g, 5.0 mmol). After
appropriate work-up, complex 10h was obtained as a colourless
oil.
Yield: 2.93 g (4.89 mmol, 97 % based on silver(I) pyruvate).
Elemental analysis: calcd. for C27H57O3AgP2 (599.56) C, 54.09;
H, 9.58 %. Found: C, 54.49; H, 9.85 %. IR (NaCl) [cm-1]: [νCO]
1701 (vs), [νCO2,as] 1601 (vs), [νCO2,s] 1418 (vs).
δ = 0.62 (t,
JHH = 7.02 Hz, 18 H, H-4), 0.99 – 1.35 (m, 36 H,
(C7), 13.61 (C4), 24.26 (d,
2
= 13.64 Hz, C ), 27.39 (d,
201.25 (C ).
H NMR (CDCl3):
3
H-1/H-2/H-3), 2.06 (s, 3 H, H-7).
6
1
31
13
C{1H} NMR (CDCl3): δ = 8.64
3
JPC = 12.38 Hz, C3), 24.93 (d,
2
1
5
1
JPC
JPC = 10.62 Hz, C ), 168.61 (C ),
1
P{ H} NMR (CDCl3): δ = -6.9. TG: one step; Tbegin =
112 °C, Tend = 398 °C, ∆m = 81.49 %. DSC: Peak 1: T = 139 °C,
∆H1 = -4.93 J/g, Peak 2: T = 233 °C, ∆H2 = 5.65 J/g, Peak 3: T
= 253 °C, ∆H3 = -86.92 J/g.
O
C7H3
C6
P(C1H2C2H2C3H2C4H3)3
O
Ag
C5
O
P(C1H2C2H2C3H2C4H3)3
101
Experimental Section
7.3.35 Synthesis of [(PnBu3)2AgO2CC(O)CH2CH3] (10i)
Complex 10i can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.02 g, 10 mmol)
was reacted with silver(I) 2-ketobutyrate (1.04 g, 5.0 mmol).
After appropriate work-up, complex 10i was obtained as a green
oil.
Yield:
2.93
g
(4.78
g,
95
%
based
on
silver(I)
2-
ketobutyrate).
Elemental analysis: calcd. for C28H59O3AgP2 (613.59) C, 54.81;
H, 9.69 %. Found: C, 54.99; H, 9.87 %. IR (NaCl) [cm-1]: [νCO]
1705 (s), [νCO2,as] 1597 (vs), [νCO2,s] 1381 (s).
= 0.69 (t,
3
1
H NMR (CDCl3): δ
JHH = 6.82 Hz, 18 H, H-4), 0.86 (t,
3
JHH = 7.27 Hz,
3 H, H-8), 1.15 – 1.42 (m, 36 H, H-1/H-2/H-3), 2.57 (q,
7.32 Hz, 2 H, H-7).
13
3
JHH =
C{1H} NMR (CDCl3): δ = 7.45 (C8), 8.45
(C7), 13.66 (C4), 24.33 (C3), 24.98 (C2), 27.55 (C1), 169.20
(C5), 205.40 (C6).
31
P{1H} NMR (CDCl3): δ = -6.6 (d,
1
J107/109Ag31P =
463 Hz). TG: one step; Tbegin = 137 °C, Tend = 401 °C, ∆m = 79.77
%. DSC: Peak 1: T = 184 °C, ∆H1 = -56.64 J/g, Peak 2: T = 213
°C, ∆H2 = -16.02 J/g, Peak 3: T = 307 °C, ∆H3 = -31.03 J/g,
Peak 4 = 361 °C, ∆H4 = -24.71 J/g.
O
C8H3C7H2
C6
O
Ag
C5
O
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
7.3.36 Synthesis of [{P(OMe)3}2AgO2CtBu] (11a)
Complex 11a can be synthesized as described in Section
7.3.14. In this respect, trimethylphosphite (1.24 g, 10 mmol)
was reacted with silver(I) pivalate (1.04, 5.0 mmol). After
appropriate work-up, complex 11a was obtained as a brown oil.
Yield: 1.91 g (4.17 mmol, 93 % based on silver(I) pivalate).
102
Experimental Section
Elemental analysis: calcd. for C11H27O8AgP2 (457.13) C, 28.95;
H,
5.97
%.
Found:
C,
28.50;
H,
5.93
1
[νCO2,as] 1559 (s), [νCO2,s] 1481 (m).
%.
JPH = 12.88 Hz, 18 H, H-1).
(CDCl3): δ = 28.79 (C4), 39.58 (C3), 51.22 (d,
31
[cm-1]:
H NMR (CDCl3): δ = 0.98 (s,
3
9 H, H-4), 3.47 (d,
C1), 185.83 (C2).
(NaCl)
IR
13
C{1H} NMR
2
JPC = 5.84 Hz,
P{1H} NMR (CDCl3): δ = 134.83. DSC: Peak 1:
T = 84 °C, ∆H1 = 5.01 J/g; Peak 2: T = 106 °C; ∆H2 = 4.13 J/g;
Peak 3: T = 182 °C; ∆H3 = -9.89 J/g.
O
(C4H3)3C3
P(OC1H3)3
Ag
C2
P(OC1H3)3
O
7.3.37 Synthesis of [{P(OMe)3}2AgO2CCMe2(OH)] (11b)
Complex 11b can be synthesized as described in Section
7.3.14. In this respect, trimethylphosphite (0.49 g, 4.0 mmol)
was reacted with silver(I) 2-hydroxyisobutyrate (0.42 g, 2.0
mmol). After appropriate work-up, complex 11b was obtained as
a green oil.
Yield:
0.90
g
(1.97
mmol,
98
%
based
on
silver(I)
2-
hydroxyisobutyrate).
Elemental analysis: calcd. for C10H25O9AgP2 (459.11) C, 26.16;
H, 5.49 %. Found: C, 26.49; H, 5.22 %. IR (NaCl) [cm-1]:
3408 (s) [νCO2,as] 1593 (vs), [νCO2,s] 1401 (vs).
= 1.31 (s, 6 H, H-3), 3.58 (d,
4.13 (s, 1 H, OH).
(d,
2
13
1
[νOH]
H NMR (CDCl3): δ
3
JPH = 12.70 Hz, 18 H, H-1),
C{1H} NMR (CDCl3): δ = 28.28 (C3), 51.40
JPC = 5.21 Hz, C1), 72.94 (C4), 183.46 (C2).
31
P{1H} NMR
(CDCl3): δ = 133.50. DSC: Peak 1: T = 62 °C, ∆H1 = 12.96 J/g;
Peak 2: T = 135 °C, ∆H2 = -38.29 J/g; Peak 3: T = 165 °C; ∆H3 =
-458.85 J/g.
103
Experimental Section
O
Ag
C2
HOC4(C3H3)2
O
P(OC1H3)3
P(OC1H3)3
7.3.38 Synthesis of [{P(OMe)3}2AgO2C(C4H3O)] (11c)
Complex 11c can be synthsized as described in Section
7.3.15. In this respect, trimethylphosphite (1.24 g, 10 mmol)
was reacted with furan-2 silver(I) carboxylate (1.09 g, 5.0
mmol). After appropriate work-up, complex 11c is obtained as a
brown solid.
Yield: 2.26 g (4.84 mmol, 96 % based on furan-2 silver(I)
carboxylate).
Mp: 45 °C. Elemental analysis: Calcd for C11H21O9AgP2 (467.10)
C, 28.29; H, 4.53 %. Found: C, 28.32; H, 4.56 %. IR (NaCl)
[cm-1]: [νC=C] 1678 (w), [νCO2,as] 1608 (vs), [νCO2,s] 1403 (vs).
NMR (CDCl3): δ = 3.77 (d,
3
JHH = 3.27 Hz,
JPH = 12.80 Hz, 18 H, H-1), 6.37 (dd,
JHH = 1.73 Hz, 1 H, H-5). 6.92 (d,
(CDCl3): δ = 51.37 (d,
H
3
3
3
JHH = 1.73 Hz, 1 H, H-6).
Hz, 1 H, H-4), 7.39 (d,
1
3
JHH = 3.27
13
C{1H} NMR
2
JPC = 5.3 Hz, C1), 111.04 (C5), 113.50
(C4), 143.47 (C3), 150.91 (C6), 182.83 (C2).
31
P{1H} NMR (CDCl3):
δ = 133.4. DSC: Peak 1: T = 42 °C, ∆H1 = 10.10 J/g; Peak 2: T =
180 °C, ∆H2 = -14.48 J/g; Peak 3: T = 181 °C, ∆H3 = 11.87 J/g;
Peak 4: T = 209 °C, ∆H2 = -13.25 J/g.
O
O
H
C
6
C5
H
C3
C4
H
Ag
C2
O
P(OC1H3)3
P(OC1H3)3
104
Experimental Section
7.3.39 Synthesis of [{P(OEt)3}2AgO2CtBu] (12a)
Complex 12a can be synthesized as described in Section
7.3.14. In this respect, trimethylphosphite (1.66 g, 10 mmol)
was reacted with silver(I) pivalate (1.04 g, 5.0 mmol). After
appropriate work-up, complex 12a was obtained as a brown oil.
Yield : 2.66 g (4.91 mmol, 98 % based on silver(I) pivalate).
Elemental analysis: calcd. for C17H39O8AgP2 (541.25) C, 37.77;
H,
7.28
%.
Found:
C,
37.90;
H,
7.37
[νCO2,as] 1557 (vs), [νCO2,s] 1418 (vs).
(s, 9 H, H-5), 0.48 – 0.53 (t,
– 3.35 (m, 12 H, H-1).
13
1
%.
IR
31
[cm-1]:
H NMR (CDCl3): δ = 0.39
3
JHH = 7.24 Hz, 18 H, H-2), 3.20
C{1H} NMR (CDCl3): δ = 16.10 (d,
6.10 Hz, C2), 28.09 (C5), 38.82 (C4), 59.94 (d,
C1), 184.37 (C3).
(NaCl)
3
JPC =
2
JPC = 6.79 Hz,
P{1H} NMR (CDCl3): δ = 130.7. DSC: Peak 1: T
= 93 °C, ∆H1 = 0.86 J/g; Peak 2: T = 187 °C, ∆H2 = -9.39 J/g;
Peak 3: T = 201 °C, ∆H3 = 6.07 J/g.
O
(C5H3)3C4
Ag
C3
O
P(OC1H2C2H3)3
P(OC1H2C2H3)3
7.3.40 Synthesis of [{P(OEt)3}2AgO2CCMe2(OH)] (12b)
Complex 12b can be synthesized as described in Section
7.3.14. In this respect, triethylphosphite (0.66 g, 4.0 mmol)
was reacted with silver(I) 2-hydroxyisobutyrate (0.42 g, 2.0
mmol). After appropriate work-up, complex 12b was obtained as
a yellow oil.
Yield:
1.05
g
(1.94
mmol,
97
%
based
on
silver(I)
2-
hydroxyisobutyrate).
Elemental analysis. calcd. for C16H37O9AgP2 (543.28) C, 35.37;
H, 6.86 %. Found: C, 35.65; H, 6.48 %. IR (NaCl) [cm-1]:
3459 (s) [νCO2,as] 1593 (vs), [νCO2,s] 1401 (vs).
= 1.19 (t,
1
[νOH]
H NMR (CDCl3): δ
3
JHH = 7.12 Hz, 18 H, H-2), 1.29 (s, 6 H, H-4), 3.46
– 4.30 (m, 12 H, H-2), 4.26 (s, 1 H, OH).
13
C{1H} NMR (CDCl3): δ
105
Experimental Section
= 16.79 (d,
3
JPC = 6.10 Hz, C2), 28.40 (C4), 60.98 (d,
6.03 Hz), 72.88 (C5), 183.65 (C3).
31
2
JPC =
P{1H} NMR (CDCl3): δ =
129.13. DSC: Peak 1: T = 150 °C, ∆H1 = -5.98 J/g; Peak 2: T =
173 °C, ∆H2 = -3.56 J/g; Peak 3: T = 202 °C; ∆H3 = -10.01 J/g.
O
Ag
C3
HOC5(C4H3)2
P(OC1H2C2H3)3
P(OC1H2C2H3)3
O
7.3.41 Synthesis of [(PnBu3)3AgO2CtBu] (13a)
Complex 13a can be synthesized as described in Section
7.3.14. In this respect, tri-n-butylphosphan (3.03 g, 15 mmol)
was reacted with silver(I) pivalate (1.04 g, 5.0 mmol). After
appropriate work-up, complex 13a was obtained as a colourless
oil.
Yield: 3.86 g (4.73 mmol, 94 % based on silver(I) pivalate).
Elemental analysis: calcd for C41H90O2AgP3 (815.95) c, 60.35; H,
11.12 %. Found: C, 60.52; H, 10.94 %. IR (NaCl) [cm-1]: [νCO2,as]
1
1569 (s), [νCO2,s] 1393 (m).
H NMR (CDCl3): δ = 0.89 (t,
3
JHH =
7.50 Hz, 27 H, H-4), 1.15 (s, 9 H, H-7), 1.38 – 1.47 (m, 54 H,
13
H-1/H-2/H-3).
C{1H} NMR (CDCl3): δ = 13.89 (C4), 24.66 (d,
3
= 12.60 Hz, C ), 26.02 (d,
1
2
2
JPC = 5.55 Hz, C ), 27.79 (d,
7
6
5
7.61 Hz, C ), 29.06 (C ), 39.67 (C ), 182.96 (C ).
31
3
JPC
1
JPC =
1
P{ H} NMR
(CDCl3): δ = -15.47. TG: one step; Tbegin = 100 °C, Tend = 350
°C, ∆m = 85.17 %. DSC: Peak 1: T = 152 °C, ∆H1 = -43.82 J/g;
Peak 2: T = 264 °C, ∆H2 = -5.27 J/g.
P(C1H2C2H2C3H2C4H3)3
O
(C7H3)3C6
Ag
C5
O
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
106
Experimental Section
7.3.42 Synthesis of [(PnBu3)3AgO2C(CH2)10CH3] (13b)
Complex 13b can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (3.03 g, 15 mmol)
was reacted with silver(I) dodecanoate (1.53 g, 5.0 mmol).
After
appropriate
work-up,
complex
was
13b
obtained
as
a
yellow oil.
Yield:
4.50
g
(4.93
mmol,
98
%
based
on
silver(I)
dodecanoate).
Elemental analysis: calcd for C48H104O2AgP3 (914.14) C, 63.07; H,
11.47 %. Found. C, 62.86; H, 11.72 %. IR (NaCl) [cm-1]: [νCO2,as]
1563 (s), [νCO2,s] 1379 (vs).
1
H NMR (CDCl3): δ = 0.84 – 0.90 (m,
30 H, H-4/H-8), 1.21 – 1.48 (m, 72 H, H-1/H-2/H-3/H-7), 2.26
(t,
3
JHH = 7.09 Hz, 2 H, H-6).
13
C{1H} NMR (CDCl3): δ = 13.65
(C4), 13.97 (C8), 22.56 (C7), 24.39 (d,
25.55 (d,
3
JPC = 12.60 Hz, C3),
2
JPC = 8.08 HZ, C2), 27.08 (C7), 29.63 (C7), 29.95
(C7), 31.82 (C7), 38.17 (C6), 178.97 (C5).
31
P{1H} NMR (CDCl3): δ
= -12.9. TG: one step; Tbegin = 100 °C, Tend = 399 °C, ∆m = 87.27
%. DSC: Peak 1: T = 149 °C, ∆H1 = -32.92 J/g; Peak 2: T = 260
°C, ∆H2 = -23.55 J/g.
P(C1H2C2H2C3H2C4H3)3
O
C8H3(C7H2)9C6H2
C5
Ag
O
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
7.3.43 Synthesis of [(PnBu3)3AgO2C(C4H3O)] (13c)
Complex 13c can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (3.03 g, 15 mmol)
was reacted with furan-2 silver(I) carboxylate (1.09 g, 5.0
mmol). After appropriate work-up, complex 13c was obtained as
a colourless oil.
Yield: 3.99 g (4.84 mmol, 96.85 % based on furan-2 silver(I)
carboxylate).
107
Experimental Section
Elemental analysis: calcd. for C41H84O3AgP3 (825.91) C, 59.63;
H, 10.25 %. Found: C, 59.74; H, 10.36 %. IR (NaCl) [cm-1]:
[νC=C] 1612 (m), [νCO2,as] 1606 (vs), [νCO2,s] 1410 (s).
(CDCl3): δ = 0.84 (t,
JHH = 6.96 Hz, 27 H, H-4), 1.30 – 1.81
3
JHH = 3.22 Hz,
3
Hz, 1 H, H-8 ), 6.81 (dd,
13
JHH = 3.22 Hz,
3
1
JHH = 1.73
JHH = 0.85 Hz, 1 H,
4
JHH = 1.73 Hz,
JHH = 0.85 Hz, 1 H, H-9).
3
2
JPC = 9.99 Hz, C2), 27.45 (d,
31
7
JPC = 12.95 Hz,
1
JPC = 5.66 Hz,
C ), 110.08 (C ), 110.94 (C ), 141.45 (C ), 153.50 (C9), 163.87
(C5).
8
3
4
C{1H} NMR (CDCl3): δ = 13.58 (C4), 24.29 (d,
C3), 25.30 (d,
H NMR
3
(m, 54 H, H-1/H-2/H-3), 6.30 (dd,
H-7), 7.32 (dd,
1
6
P{1H} NMR (CDCl3): δ = -11.6. TG: one step; Tbegin = 102
°C, Tend = 354 °C, ∆m = 85.55 %. DSC: Peak 1: T = 128 °C, ∆H1 =
-12.53 J/g; Peak 2: T = 192 °C, ∆H2 = 20.25 J/g; Peak 3: T =
213 °C, ∆H3 = 11.55 J/g; Peak 4: T = 293 °C, ∆H4 = 1.69 J/g.
P(C1H2C2H2C3H2C4H3)3
O
O
H
9
C
C8
Ag
C5
C6
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
O
C7
H
H
7.3.44 Synthesis of [(PnBu3)3AgO2CCH=CH(C4H3O)] (13d)
Complex 13d can be synthesized as described in Section
7.3.15.
In
this
respect,
tri-n-butylphosphan
(1.21
g,
6.0
mmol), was reacted with silver(I) furylacrylate (0.48 g, 2.0
mmol). After appropriate work-up, complex 13d was obtained as
a brown oil.
Yield:
1.67
g
(1.96
mmol,
98
%
based
on
silver(I)
furylacrylate).
Elemental analysis: calcd. for C43H86O3AgP3 (851.94) C, 60.62;
H, 10.17 %. Found: C, 60.96; H, 10.42 %. IR (NaCl) [cm-1]:
[νC=C] 1693 (s), [νCO2,as] 1551 (s), [νCO2,s] 1371 (vs).
1
H NMR
108
Experimental Section
3
(CDCl3): δ = 0.88 (t,
JHH = 7.20 Hz, 27 H, H-4), 1.31 – 1.57
3
(m, 57 H, H-1/H-2/H-3), 6.35 (dd,
Hz, 1 H, H-10), 6.42 (d,
JHH = 1.80 Hz,
JHH = 15.60 Hz, 1 H, H-9), 6.51 (d,
JHH = 15.60 Hz, 1 H, H-6), 7.34 (d,
JHH = 15.60 Hz, 1 H, H-7),
JHH = 1.80 Hz, 1 H, H-11).
Hz, C2), 27.63 (d,
(C10),
3
3
13.78 (C4), 24.50 (d,
(C6),
122.56
170.65 (C5).
31
JHH = 3.30
3
3
7.35 (d,
3
13
C{1H} NMR (CDCl3): δ =
3
JPC = 12.38 Hz, C3), 25.61 (d,
2
JPC = 6.85
1
JPC = 5.78 Hz, C1), 111.17 (C9), 111.56
(C7),
127.61
142.97
(C11),
(C8),
152.64
P{1H} NMR (CDCl3): δ = -14.18. DSC: Peak 1 = 154
°C, ∆H1 = 5.17 J/g; Peak 2 = 190 °C, ∆H2 = -2.11 J/g; Peak 3 =
242 °C, ∆H3 = -15.46 J/g; Peak 4 = 260 °C, ∆H4 = -1.54 J/g.
P(C1H2C2H2C3H2C4H3)3
O
O
H
C11
C8
C10
C7H
Ag
C5
C6H
O
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
C9
H
H
7.3.45 Synthesis of [(PnBu3)3AgO2CC(O)CH3] (13e)
Complex 13e can be synthesized as described in Section
7.3.15.
In
this
respect,
tri-n-butylphosphan
(1.21
g,
6.0
mmol), was reacted with silver(I) pyruvate (0.38 g, 2.0 mmol).
After
appropriate
work-up,
complex
13e
was
obtained
as
a
colourless oil.
Yield: 1.57 g (1.96 mmol, 98 % based on silver(I) pyruvate).
Elemental analysis: calcd. for C39H84O3AgP3 (801.88) C, 58.42;
H, 10.56 %. Found: C, 58.53; H, 10.24 %. IR (NaCl) [cm-1]: [νCO]
1702 (s), [νCO2,as] 1611 (vs), [νCO2,s] 1414 (s).
= 0.89 (t,
1
H NMR (CDCl3): δ
3
JHH = 6.96 Hz, 27 H, H-4), 1.37 – 1.70 (m, 54 H, H-
1/H-2/H-3), 2.34 (s, 3 H, H-7).
(C7), 13.73 (C4), 24.44 (d,
= 9.93 Hz, C2), 27.55 (d,
204.54 (C6).
31
3
13
C{1H} NMR (CDCl3): δ = 13.36
JPC = 12.82 Hz, C3), 25.40 (d,
2
JPC
1
JPC = 5.09 Hz, C1), 169.17 (C5),
P{1H} NMR (CDCl3): δ = -11.5. TG: one step; Tbegin
109
Experimental Section
= 101 °C, Tend = 369 °C, ∆m = 85.99 %.
DSC: Peak 1: T = 253
°C, ∆H1 = 10.16 J/g.
O
C6
C7 H3
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
O
Ag
C5
O
7.3.46 Synthesis of [(PnBu3)3AgO2CC(O)CH2CH3] (13f)
Complex 13f can be synthesized as described in Section
7.3.15.
In
this
tri-n-butylphosphan
respect,
(1.21
g,
6.0
mmol), was reacted with silver(I) 2-ketobutyrate (0.41 g, 2.0
mmol). After appropriate work-up, complex 13f is obtained as a
green oil.
Yield:
1.57
g
(1.92
mmol,
96
%
based
on
silver(I)
2-
ketobutyrate).
Elemental analysis: calcd. for C40H86O3AgP3 (815.91) C, 58.88;
H, 10.62 %. Found: C, 59.12; H, 10.31 %. IR (NaCl) [cm-1]: [νCO]
1703 (s), [νCO2,as] 1608 (vs), [νCO2,s] 1411 (s).
3
= 0.80 (t, JHH = 6.72 Hz, 27 H, H-4), 0.95 (t,
1
H NMR (CDCl3): δ
3
JHH = 7.35 Hz, 3
H, H-8), 1.27 – 1.75 (m, 54 H, H-1/H-2/H-3), 2.67 (q,
7.32 Hz, 2 H, H-7).
13
3
= 10.06 Hz, C2), 27.65 (d,
31
JHH =
C{1H} NMR (CDCl3): δ = 7.65 (C8), 13.25
(C7), 13.81 (C4), 24.52 (d,
206.73 (C6).
3
JPC = 12.82 Hz, C3), 25.47 (d,
1
2
JPC
JPC = 5.47 Hz, C1), 169.76 (C5),
P{1H} NMR (CDCl3): δ = -11.3. TG: one step; Tbegin
= 103 °C, Tend = 350 °C, ∆m = 85.03 %. DSC: Peak 1: T = 139 °C,
∆H1 = 6.50 J/g; Peak 2: T = 229 °C, ∆H2 = 10.73 Hz.
O
C8H3C7H2
C6
O
Ag
C5
O
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
110
Experimental Section
7.3.47 Synthesis of [{P(OMe)3}3AgO2CtBu] (14a)
Complex 14a can be synthesized as described in Section
7.3.14. In this respect, trimethylphosphite (1.86 g, 15 mmol),
was reacted with silver(I) pivalate (1.04 g, 5.0 mmol). After
appropriate work-up, complex 14a was obtained as a colourless
oil.
Yield: 2.87 g (4.94 mmol, 98 % based on silver(I) pivalate).
Elemental analysis: calcd. for C14H36O11AgP3 (581.21) C, 28.96;
H,
6.25
%.
Found:
C,
28.60;
H,
6.08
[νCO2,as] 1559 (vs), [νCO2,s] 1410 (s).
(s, 9 H, H-4), 3.17 (d,
3
1
%.
31
[cm-1]:
H NMR (CDCl3): δ = 0.78
JPH = 12.57 Hz, 27 H, H-1),
(CDCl3): δ = 28.32 (C4), 39.04 (C3), 50.50 (d,
C1), 184.14 (C2).
(NaCl)
IR
2
13
C{1H} NMR
JPC = 5.66 Hz,
P{1H} NMR (CDCl3): δ = 135.4. DSC: Peak 1: T
= 102 °C, ∆H1 = 7.43 J/g; Peak 2: T = 174 °C, ∆H2 = -9.98 Hz.
O
(C4H3)3C3
Ag
C2
O
P(OC1H3)3
P(OC1H3)3
P(OC1H3)3
7.3.48 Synthesis of [{P(OMe)3}3AgO2CCMe2(OH)] (14b)
Complex 14b can be synthesized as described in Section
7.3.14. In this respect, trimethylphosphite (0.55 g, 4.5 mmol)
was reacted with silver(I) 2-hydroxyisobutyrate (0.31 g, 1.5
mmol). After appropriate work-up, complex 14b was obtained as
a brown oil.
Yield:
0.85
g
(1.47
mmol,
98
%
based
on
silver(I)
2-
hydroxyisobutyrate).
Elemental analysis: cacld. for C13H34O12AgP3 (583.20) C, 26.77;
H, 5.88 %. Found: C, 26.31; H, 5.92 %. IR (NaCl) [cm-1]:
3416 (s) [νCO2,as] 1581 (s), [νCO2,s] 1400 (m).
1.09 (s, 6 H, H-3), 3.52 (d,
(s, 1 H, OH).
13
3
1
[νOH]
H NMR (CDCl3): δ =
JPH = 12.57 Hz, 27 H, H-1 ), 4.34
C{1H} NMR (CDCl3): δ = 28.09 (C3), 50.94 (d,
2
JPC
111
Experimental Section
= 5.21 Hz, C1), 72.56 (C4), 182.64 (C2).
31
P{1H} NMR (CDCl3): δ =
134.38. TG: one step; Tbegin = 79 °C, Tend = 302 °C, ∆m = 84.82
%. DSC: Peak 1: T = 81 °C, ∆H1 = 1.18 J/g; Peak 2: T = 104 °C,
∆H2 = 3.18 Hz.
P(OC1H3)3
P(OC1H3)3
P(OC1H3)3
O
Ag
C2
HOC4(C3H3)2
O
7.3.49 Synthesis of [{P(OEt)3}3AgO2CtBu] (15a)
Complex 15a can be synthesized as described in Section
7.3.14. In this respect, triethylphosphite (2.50 g, 15 mmol)
was reacted with silver(I) pivalate (1.04 g, 5.0 mmol). After
appropriate work-up, complex 15a was obtained as a colourles
oil.
Yield: 3.40 g ( 4.80 mmol, 96 % based on silver(I) pivalate).
Elemental analysis: calcd. for C23H54O11AgP3 (707.38) C, 39.08;
H,
7.71
%.
Found:
C,
38.83;
H,
7.61
[νCO2,as] 1559 (s), [νCO2,s] 1392 (m).
3
9 H, H-5), 0.65 – 0.71 (t,
3.58 (m, 18 H, H-1).
13
2
5
1
%.
IR
31
[cm-1]:
H NMR (CDCl3): δ = 0.55 (s,
JHH = 7.07 Hz, 27 H, H-2), 3.36 –
1
C{ H} NMR (CDCl3): δ = 16.32 (d,
4
5.98 Hz, C ), 28.38 (C ), 39.60 (C ), 59.66 (d,
C1), 189.63 (C3).
(NaCl)
2
3
JPC =
JPC = 7.08 Hz,
P{1H} NMR (CDCl3): δ = 132.20. DSC: Peak 1:
T = 49 °C, ∆H1 = 0.14 J/g; Peak 2: T = 175 °C, ∆H2 = .-1.97 J/g
; Peak 3: T = 186 °C, ∆H3 = -4.25 Hz.
O
(C5H3)3C4
Ag
C3
O
P(OC1H2C2H3)3
P(OC1H2C2H3)3
P(OC1H2C2H3)3
112
Experimental Section
7.3.50 Synthesis of [{P(OEt)3}3AgO2CCMe2(OH)] (15b)
Complex 15b can be synthesized as described in Section
7.3.14. In this respect, triethylphosphite (0.74 g, 4.5 mmol)
was reacted with silver(I) 2-hydroxyisobutyrate (0.31 g, 1.5
mmol). After appropriate work-up, complex 15b was obtained as
a green oil.
Yield.
1.03
g
(1.45
mmol,
96
%
based
on
silver(I)
2-
hydroxyisobutyrate).
Elemental analysis: calcd. for C22H52O12AgP3 (709.44) C, 37.25;
H, 7.39 %. Found: C, 36.87; H, 7.85 %. IR (NaCl) [cm-1]:
3457 (s) [νCO2,as] 1592 (s), [νCO2,s] 1392 (vs).
= 1.20 (t,
3.87-3.99
3
2
H NMR (CDCl3): δ
JPH = 7.09 Hz, 27 H, H-2), 1.29 (s, 6 H, H-4),
(m,
18
H,
H-2),
(CDCl3): δ = 16.65 (d,
(d,
1
[νOH]
3
4.70
(s,
1
H,
OH).
13
C{1H}
NMR
JPC = 5.91 Hz, C2), 28.15 (C4), 60.12
JPC = 6.60 Hz, C1), 72.57 (C5), 182.60 (C3).
31
P{1H} NMR
(CDCl3): δ = 131.28. DSC: Peak 1: T = 83 °C, ∆H1 = 0.35 J/g;
Peak 2: T = 159 °C, ∆H2 = -2.59 Hz.
P(OC1H2C2H3)3
O
HOC5(C4H3)2
P(OC1H2C2H3)3
P(OC1H2C2H3)3
Ag
C3
O
7.3.51. Synthesis of [(nBu3P)2AgO2CCH2CO2Ag(PnBu3)2] (16a)
Complex 16a can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.42 g, 12 mmol)
was reacted with silver(I) malonate (0.95 g, 3.0 mmol). After
appropriate work-up, complex 16a was obtained as a brown oil.
Yield: 2.92 g (2.59 mmol, 86 % based on silver(I) malonate).
Elemental analysis: calcd. for C51H110O4Ag2P4 (1127.06) C, 54.35;
H,
9.84
%.
Found:
C,
54.97;
H,
9.82
[νCO2,as] 1558 (vs), [νCO2,s] 1417 (s).
(t,
3
1
%.
IR
(NaCl)
[cm-1]:
H NMR (CDCl3): δ = 0.87
JHH = 6.60 Hz, H-4), 1.39 – 1.58 (m, 72 H, H-1/H-2/H-3),
113
Experimental Section
3.16 (s, 2 H, H-6).
(C6), 24.36 (d,
3
13
C{1H} NMR (CDCl3): δ = 13.69 (C4), 18.90
JPC = 12.69 Hz, C3), 25.05 (d,
C2), 27.63 (C1), 174.25 (C5).
31
2
JPC = 14.43 Hz,
P{1H} NMR (CDCl3): δ = -6.84. TG:
one step; Tbegin = 100 °C, Tend = 315 °C, ∆m = 79.27 %. DSC: Peak
1: T = 74 °C, ∆H1 = 1.85 J/g; Peak 2: T = 145 °C, ∆H2 = -12.60
J/g; Peak 3: T = 234 °C, ∆H3 = 11.47 J/g; Peak 4: T = 352 °C,
∆H4 = -6.86 J/g.
O
(C4H3C3H2C2H2C1H2)3P
(C4H
3
C3 H
2
C2 H
2
C1 H
O
C5 C6 H2 C5
Ag
2 )3 P
P(C1H2C2H2C3H2C4H3)3
O
Ag
O
P(C1H2C2H2C3H2C4H3)3
7.3.52 Synthesis of [(nBu3P)3AgO2CCH2CO2Ag(PnBu3)3] (16b)
Complex 16b can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (3.64 g, 18 mmol)
was reacted with silver(I) malonate (0.95 g 3.0 mmol). After
appropriate work-up, complex 16b was obtained as a colourless
oil.
Yield: 4.08 g (2.66 mmol, 88 % based on silver(I) malonate).
Elemental analysis: calcd. for C75H164O4Ag2P6 (1531.70) C, 58.81;
H, 10.79 %. Found: C, 58.59; H, 10.62 %. IR (NaCl) [cm-1]:
[νCO2,as] 1552 (vs), [νCO2,s] 1416 (s).
(t,
3
H NMR (CDCl3): δ = 0.86
JHH = 6.65 Hz, 54 H, H-4), 1.34 – 1.56 (m, 108 H, H-1/H-
2/H-3), 3.06 (s, 2 H, H-6).
19.16 (C6), 24.61 (d,
13
3
C{1H} NMR (CDCl3): δ = 13.86 (C4),
JPC = 12.90 Hz, C3), 25.35 (d,
11.89 Hz, C2), 27.64 (d,
31
1
1
2
JPC =
JPC = 4.53 Hz, C1), 173.42 (C5).
P{1H} NMR (CDCl3): δ = -9.5. TG: one step; Tbegin = 99 °C, Tend
= 356 °C, ∆m = 85.72 %. DSC: Peak 1: T = 154 °C, ∆H1 = 6.62
J/g; Peak 2: T = 165 °C, ∆H2 = 7.07 J/g; Peak 3: T = 284 °C,
∆H3 = -65.32 J/g.
114
Experimental Section
O
(C4H3C3H2C2H2C1H2)3P
(C4H3C3H2C2H2C1H2)3P
O
C5 C6 H2 C5
Ag
P(C1H2C2H2C3H2C4H3)3
Ag
O
(C4H3C3H2C2H2C1H2)3P
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
O
7.3.53 Synthesis of [(nBu3P)2AgO2CCH2CH2CO2Ag(PnBu3)2] (16c)
Complex 16c can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (2.42 g, 12 mmol)
was reacted with silver(I) succinate (0.99 g, 3.0 mmol). After
appropriate work-up, complex 16c was obtained as a brown oil.
Yield: 2.86 g (2.51 g, 83 % based on silver(I) succinate).
Elemental analysis: calcd. for C52H112O4Ag2P4 (1141.09) C, 54.73;
H,
9.89
%.
Found:
C,
54.94,
H,
9.81
[νCO2,as] 1555 (vs), [νCO2,s] 1383 (s).
(t,
3
1
%.
IR
(NaCl)
[cm-1]:
H NMR (CDCl3): δ = 0.63
JHH = 6.80 Hz, 36 H, H-4), 1.11 – 1.30 (m, 72 H, H-1/H-
2/H-3), 2.28 (s, 4 H, H-6).
24.56 (d,
3
13
C{1H} NMR (CDCl3): δ = 13.89 (C4),
JPC = 11.91 Hz, C3), 25.39 (d,
25.76 (C6), 27.66 (C1), 179.32 (C5).
31
2
JPC = 11.71 Hz, C2),
P{1H} NMR (CDCl3): δ = -
7.87. TG: one step; Tbegin = 125 °C, Tend = 480 °C, ∆m = 80.62 %.
DSC: Peak 1: T = 86 °C, ∆H1 = 2.62 J/g; Peak 2: T = 243 °C, ∆H2
= 15.11 J/g; Peak 3: T = 274 °C, ∆H3 = -5.27 J/g.
(C4H3C3H2C2H2C1H2)3P
(C4H3C3H2C2H2C1H2)3P
O
O
C 5C 6H 2C 6H 2C 5
Ag
O
Ag
O
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
7.3.54 Synthesis of [(nBu3P)3AgO2CCH2CH2CO2Ag(PnBu3)3] (16d)
Complex 16d can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (3.64 g, 18 mmol)
was reacted with silver(I) succinate (0.99 g, 3.0 mmol). After
appropriate work-up, complex 16d was obtained as a colourless
oil.
115
Experimental Section
Yield: 4.06 g (2.62 mmol, 87 % based on silver(I) succinate).
Elemental analysis: calcd. for C76H166O4Ag2P6 (1545.73) C, 59.06;
H, 10.82 %. Found: C, 59.33; H, 11.01 %. IR (NaCl) [cm-1]:
[νCO2,as] 1561 (vs), [νCO2,s] 1376 (s).
(t,
3
1
H NMR (CDCl3): δ = 0.83
JHH = 6.54 Hz, 54 H, H-4), 1.33 – 1.45 (m, 108 H, H-1/H-
2/H-3), 2.47 (s, 4 H, H-6).
24.34 (d,
3
13
C{1H} NMR (CDCl3): δ = 13.57 (C4),
JPC = 11.48 Hz, C3), 23.63 (C6), 25.27 (C2), 27.26
(C1), 177.29 (C5).
31
P{1H} NMR (CDCl3): δ = -14.4. TG: one step;
Tbegin = 101 °C, Tend = 349 °C, ∆m = 83.89 %.. DSC: Peak 1: T =
264 °C, ∆H1 = -83.65 J/g; Peak 2: T = 273 °C, ∆H2 = 41.41 J/g.
O
(C4H3C3H2C2H2C1H2)3P
(C4H3C3H2C2H2C1H2)3P
O
C5C6H2C6H2C5
Ag
O
(C4H3C3H2C2H2C1H2)3P
P(C1H2C2H2C3H2C4H3)3
Ag
P(C1H2C2H2C3H2C4H3)3
P(C1H2C2H2C3H2C4H3)3
O
7.3.55 Synthesis of [(nBu3P)AgO2C(C4H2S)CO2Ag(PnBu3)] (16e)
Complex 16e can be synthesized as described in Section
7.3.15.
In
this
respect,
tri-n-butylphosphan
(0.80
g,
4.0
mmol) was reacted with thiophene-2,5 silver(I) dicarboxylate
(0.77 g, 2 mmol). After appropriate work-up complex 16e was
obtained as a
Yield:
1.35
brown oil.
g
(1.70
mmol,
85
%
based
on
thiophene-2,5
silver(I) dicarboxylate).
Elemental analysis: calcd. for C30H56O4SAg2P2 (790.52) C, 45.58;
H, 7.14; S, 4.06 %. Found: C, 46.14; H, 7.73; S, 3.85 %. IR
(NaCl)
[cm-1]:
[νCO2,as]
(CDCl3): δ = 0.77 (t,
1696
3
(s),
[νCO2,s]
(vs).
1
H
NMR
JHH = 6.79 Hz, H-4), 1.15 – 1.53 (m, 36
H, H-1/H-2/H-3), 7.45 (s, 2 H, H-7).
13.71 (C4), 24.53 (d,
1457
3
13
C{1H} NMR (CDCl3): δ =
JPC = 23.83 Hz, C3), 25.63 (C2), 27.79
(C1), 131.37 (C7), 143.14 (C6), 167.67 (C5).
31
P{1H} NMR (CDCl3):
116
Experimental Section
δ = -4.62. DSC: Peak 1: T = 85 °C, ∆H1 = 0.33 J/g; Peak 2: T =
182 °C, ∆H2 = 12.28 J/g; Peak 3: T = 256 °C, ∆H3 = -85.51 J/g.
O
O
(C4H3C3H2C2H2C1H2)3P
Ag
S
C5
C6
O
C6
C7
P(C1H2C2H2C3H2C4H3)3
Ag
C5
O
C7
H
H
7.3.56 Synthesis of [(nBu3P)2AgO2C(C4H2S)CO2Ag(PnBu3)2] (16f)
Complex 16f can be synthesized as described in Section
7.3.15. In this respect, tri-n-butylphosphan (1.61 g, 8 mmol)
was reacted with thiophene-2,5 silver(I) dicarboxylate (0.77
g,
2
mmol).
After
appropriate
was
work-up,
complex
%
on
thiophene-2,5
for
C54H110O4SAg2P4
16f
obtained as a white solid.
Yield:
2.12
g
(1.78
mmol,
89
based
silver(I) dicarboxylate).
Mp:
42
°C.
Elemental
analysis:
calcd.
(1195.16) C, 54.27; H, 9.28; S, 2.68 %. Found: C, 54.41; H,
9.19; S, 2.37 %. IR (NaCl) [cm-1]: [νCO2,as] 1686 (s), [νCO2,s]
1459 (vs).
1
H NMR (CDCl3): δ = 0.88 (t,
3
JHH = 6.65 Hz, 36 H, H-
4), 1.26 – 1.83 (m, 72 H, H-1/H-2/H-3), 7.58 (s, 2 H, H-7).
13
C{1H} NMR (CDCl3): δ = 13.89 (C4), 24.60 (d,
C3), 25.39 (d,
2
3
JPC = 10.75 Hz, C2), 27.67 (d,
C1), 131.21 (C7), 143.38 (C6), 165.78 (C5).
31
JPC = 12.82 Hz,
1
JPC = 5.15 Hz,
P{1H} NMR (CDCl3):
δ = -11.00. DSC: Peak 1. T = 194 °C, ∆H1 = 3.27 J/g; Peak 2: T
= 258 °C, ∆H2 = -59.18 J/g.
(C4H3C3H2C2H2C1H2)3P
O
Ag
(C4H3C3H2C2H2C1H2)3P
[P(C1H2C2H2C3H2C4H3)3]2
O
S
C5
C6
O
C7
H
Ag
C5
C6
O
C7
H
[P(C1H2C2H2C3H2C4H3)3]2
117
Experimental Section
7.3.57 Synthesis of [HO-2-(C6H4)C(H)N(C6H4)-4-OMe] (19a)
p-Anisidine (6.15 g, 50 mmol) was dissolved in 150 mL of
ethanol and 2-hydroxybenzaldehyd (6.11 g, 50 mmol) was added.
The reaction mixture was refluxed at 100 °C for 4 h. The
product which cristallises on cooling was filtered, off washed
with cold ethanol and dried under oil-pump vacuo. Complex 19a
was obtained as a green solid.
Yield: 9.74 g (42.8 mmol, 85 % based on P-anisidine).
Mp: 82 °C. Elemental analysis: calcd. for C14H13O2N (227.26) C,
73.99; H, 5.77; N, 6.16 %. Found: C, 73.78; H, 5.79; N, 6.13
%. IR (KBr) [cm-1]: [νC=N] 1622 (s), [νC=C] 1570 (s).
1
H NMR
(CDCl3): δ = 3.84 (s, 3 H, CH3), 6.90 – 7.38 (m, 8 H, H-Ph),
8.92 (s, 1 H, CH=N), 13.41 (s, 1 H, OH).
13
C{1H} NMR (CDCl3): δ
= 55.95 (OCH3), 117.56 (C-Ph), 119.37 (C-Ph), 119.80 (C-Ph),
122.70 (C-Ph), 132.35 (C-Ph), 133.07 (C-Ph), 141.82 (C-Ph),
159.26 (C-Ph), 160.86 (C-Ph), 161.41 (C=N).
OH
C
N
OCH3
H
7.3.58 Synthesis of [HO-2-(C6H4)C(H)N(C6H4)-4-Me] (19b)
Complex 19b can be synthesized as described in section
7.3.57. In this respect, P-toluidine (5.35 g, 50 mmol) was
reacted
with
appropriate
2-hydroxybenzaldehyd
work-up,
complex
19b
(6.11
was
g,
50
obtained
mmol).
as
solid.
Yield: 9.15 g (43.32 mmol, 86 % based on P-toluidine).
a
After
yellow
118
Experimental Section
Mp: 89 °C. Elemental analysis: calcd. for C14H13ON (211.26) C,
79.59; H, 6.20; N, 6.63 %. Found: C, 79.10; H, 6.59; N, 6.12
%. IR (KBr) [cm-1]: [νC=N] 1617 (s), [νC=C] 1597 (s).
1
H NMR
(CDCl3): δ = 2.39 (s, 3 H, CH3), 6.90 – 7.40 (m, 8 H, H-Ph),
8.61 (s, 1 H, CH=N), 13.41 (s, 1 H, OH).
13
C{1H} NMR (CDCl3): δ
= 21.40 (CH3), 117.63 (C-Ph), 119.41 (C-Ph), 119.75 (C-Ph),
121.44 (C-Ph), 130.44 (C-Ph), 132.56 (C-Ph), 133.32 (C-Ph),
137.33 (C-Ph), 146.29 (C-Ph), 161.56 (C-Ph), 162.10 (C=N).
OH
C
N
CH3
H
7.3.59 Synthesis of [Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}] (20a)
Silver(I) nitrate (0.84 g, 5.0 mmol) dissolved in 30 mL of
ethanol mixed with 2 mL of acetonitril was added to [HO-2(C6H4)C(H)N(C6H4)-4-OMe] (1.13 g, 5.0 mmol) dissolved in 30 mL
ethanol at 0 °C. After stirring for 5 min, triethylamine (0.50
g, 5 mmol) dissolved in 5 mL of ethanol was added dropwise.
The
reaction
mixture
was
stirred
for
4
h;
the
green
precipitate obtained was filtered, washed three times with 5
mL of ethanol and dried. Complex 20a was obtained as a green
solid, which is not soluble in organic solvents.
Yield: 0.63 g (1.88 mmol, 37 % based on silver(I) nitrate).
Mp: 110 °C (decomp.). Elemental analysis: calcd. for C14H12O2Nag
(334.12) C, 50.33; H, 3.62; N, 4.19 %. Found: C, 50.68; H,
3.68; N, 4.48 %. IR (KBr) [cm-1]: [νC=N] 1622 (s), [νC=C] 1567
(w).
119
Experimental Section
7.3.60 Synthesis of [Ag{O-2-(C6H4)C(H)N(C6H4)-4-Me}] (20b)
Complex 20b can be synthesized as described in Section
7.3.59. In this respect, silver(I) nitrate (0.84 g, 5.0 mmol)
was
reacted
with
[HO-2-(C6H4)C(H)N(C6H4)-4-Me]
(1.05
g,
5.0
mmol) and triethylamine (0.50 g, 5 mmol). After appropriate
work-up, complex 20b was obtained as a yellow solid, which is
not soluble in organic solvents.
Yield: 0.62 g (1.97 mmol, 39 % based on silver(I) nitrate).
Mp: 94 °C (decomp.). Elemental analysis: calcd. for C14H12ONAg
(318.12) C, 52.86; H, 3.80; N, 4.40 %. Found: C, 52.49, H,
3.67; N, 4.44 %. IR (KBr) [cm-1]: [νC=N] 1618 (s), [νC=C] 1567
(w).
7.3.61
Synthesis
[(PnBu3)Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}]
of
(21a)
Complex 21a can be synthesized as described in Section
7.3.14.
In
this
respect
tri-n-butylphosphane
(0.30
g,
1.5
mmol) was reacted with [Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}] (20a)
(0.50 g, 1.5 mmol). After appropriate work-up, complex 21a was
obtained as a green solid.
Yield: 0.78 g (1.46 mmol, 97 % based on 20a).
Mp: 88 °C. Elemental analysis: calcd. for C26H39O2NagP (536.44)
C, 58.21; H, 7.33; N, 2.61 %. Found: C, 58.61; H, 7.24; N,
2.86 %. IR (KBr) [cm-1]: [νC=N] 1618 (s), [νC=C] 1573 (w).
(CDCl3): δ = 0.86 (t,
3
1
H NMR
JHH = 6.67 Hz, 9 H, H-4), 1.37 – 1.58 (m,
18 H, H-1/H-2/H-3), 3.81 (s, 3 H, H-5), 6.87 – 7.25 (m, 8 H,
H-Ph), 8.29 (s, 1 H, CH=N).
24.45 (d,
3
28.23 (d,
1
13
C{1H} NMR (CDCl3): δ = 13.57 (C4),
JPC = 14.67 Hz, C3), 25.84 (d,
2
JPC = 19.85 Hz, C2),
JPC = 5.42 Hz, C1), 55.33 (C5), 108.42 (C-Ph), 112.16
(C-Ph), 114.65 (C-Ph), 120.45 (C-Ph), 123.03 (C-Ph), 123.65
(C-Ph), 133.05 (C-Ph), 136.77 (C-Ph), 147.63 (C-Ph), 158.12
(C-Ph), 166.23 (C=N).
31
P{1H} NMR (CDCl3): δ = -1.7 (d,
1
J107Ag/31P
= 729.56 Hz), -1.70 (d,1J109Ag/31P = 648.00 Hz). TG: one steps;
120
Experimental Section
Tbegin = 102 °C, Tend = 519 °C, ∆m = 73.10 %. DSC: Peak 1: T = 49
°C, ∆H1 = 4.32 J/g; Peak 2: T = 79 °C, ∆H2 = 37.53 J/g; Peak 3:
T = 192 °C, ∆H3 = -42.57 J/g.
P(C1H2C2H2C3H2C4H3)3
O
Ag
C
OC5H3
N
H
7.3.62
Synthesis
[(PnBu3)Ag{O-2-(C6H4)C(H)N(C6H4)-4-Me}]
of
(21b)
Complex 21b can be synthesized as described in Section
7.3.14.
In
this
tri-n-butylphosphane
respect
(0.30
g,
1.5
mmol) was reacted with [Ag{O-2-(C6H4)C(H)N(C6H4)-4-Me}] (20b)
(0.47 g, 1.5 mmol). After appropriate work-up, complex 21b was
obtained as a yellow solid.
Yield: 0.76 g (1.46 mmol, 98.% based on 20b).
Mp: 90 °C. Elemental analysis: calcd. for C26H39ONAgP (520.44)
C, 60.00; H, 7.55; N, 2.69 %. Found. C, 59.66; H, 7.63; N,
2.64 %. IR (KBr) [cm-1]: [νC=N] 1618 (s), [νC=C] 1598 (m).
(CDCl3): δ = 0.87 (t,
3
1
H NMR
JHH = 7.11 Hz, 9 H, H-4), 1.35 – 1.56 (m,
18 H, H-1/H-2/H-3), 2.34 (s, 1 H, H-5), 6.80 – 7.20 (m, 8 H,
H-Ph), 8.27 (s, 1 H, CH=N).
13
C{1H} NMR (CDCl3): δ = 13.56 (C4),
20.41 (C5), 24.47 (d,3JPC = 14.64 Hz, C3), 25.87 (d,
Hz, C2), 28.23 (d,
1
2
JPC = 19.65
JPC = 5.47 Hz, C1), 111.21 (C-Ph), 120.43
(C-Ph), 122.02 (C-Ph), 124.46 (C-Ph), 129.94 (C-Ph), 133.20
(C-Ph), 134.71 (C-Ph), 137.30 (C-Ph), 152.69 (C-Ph), 167.47
(C-Ph),
1
174.54
(C=N).
31
P{1H}
NMR
(CDCl3):
δ
=
-2.1
(bd,
J107/109Ag31P = 673.00 Hz). TG: one steps; Tbegin = 153 °C, Tend =
121
Experimental Section
401 °C, ∆m = 73.45 %. DSC: Peak 1: T = 89 °C, ∆H1 = 12.01 J/g,
Peak 2: T = 218 °C, ∆H2 = -68.96 J/g.
P(C1H2C2H2C3H2C4H3)3
O
Ag
C
C5H3
N
H
7.3.63
Synthesis
[(PnBu3)Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}]
of
(21c)
Complex 21c can be synthesized as described in Section
7.3.14.
In
this
respect
tri-n-butylphosphane
(0.60
g,
3.0
mmol) was reacted with [Ag{O-2-(C6H4)C(H)N(C6H4)-4-OMe}] (20a)
(0.50 g, 1.5 mmol). After appropriate work-up, complex 21c is
obtained as a black oil.
Yield: 1.08 g (1.46 mmol, 98 % based on 20a)
Elemental analysis: calcd. for C38H66O2NagP2 (738.76) C, 61.78;
H, 9.00; N, 1.90 %. Found: C, 61.58; H, 8.99; N, 1.86 %. IR
(KBr) [cm-1]: [νC=N] 1610 (s), [νC=C] 1502 (s).
= 0.89 (t,
3
1
H NMR (CDCl3): δ
JHH = 6.87 Hz, 18 H, H-4), 1.21 – 1.60 (m, 36 H, H-
1/H-2/H-3), 3.82 8s, 3 H, H-5), 6.87 – 7.36 (m, 8 H, H-Ph),
8.58 (s, 1 H, CH=N).
(d,
3
13
C{1H} NMR (CDCl3): δ = 14.14 (C4), 24.81
JPC = 12.69 Hz, C3), 25.42 (d,
2
JPC = 13.13 Hz, C2), 27.95
(C1), 55.92 (C5), 109.72 (C-Ph), 114.99 (C-Ph), 117.41 (C-Ph),
119.42 (C-Ph), 119.81 (C-Ph), 122.67 (C-Ph), 132.38 (C-Ph),
133.00
31
(C-Ph),
141.95
(C-Ph),
159.22
(C-Ph),
160.80
(C=N).
P{1H} NMR (CDCl3): δ = -8.2. TG: one steps; Tbegin = 107 °C,
Tend = 499 °C, ∆m = 81.14 %. DSC: Peak 1: T = 149 °C, ∆H1 = 6.72
J/g, Peak 2: T = 208 °C, ∆H2 = -88.13 J/g; Peak 3: T = 225 °C,
∆H3 = 5.31 J/g.
122
Experimental Section
P(C1H2C2H2C3H2C4H3)3
O
Ag
C
P(C1H2C2H2C3H2C4H3)3
OC5H3
N
H
7.3.64
Synthesis
of
[(PnBu3)2Ag{O-2-(C6H4)C(H)N(C6H4)-4-Me}]
(21d)
Complex 21d can be synthesized as described in Section
7.3.14.
mmol)
In
this
was
respect
reacted
with
tri-n-butylphosphane
(0.60
[Ag{O-2-(C6H4)C(H)N(C6H4)4-Me}]
g,
3.0
(20b)
(0.47 g, 1.5 mmol). After appropriate work-up, complex 21d was
obtained as a brown oil.
Yield: 1.05 g (1.45 mmol, 96 % based on 20b)
Elemental analysis: calcd for C38H66ONAgP2 (722.76) C, 63.15; H,
9.22; N, 1.94 %. Found: C, 63,36; H, 9.22; N, 2.19 %. IR (KBr)
[cm-1]: [νC=N] 1595 (s), [νC=C] 1508 (s).
(t,
3
1
H NMR (CDCl3): δ = 0.86
JHH = 7.30 Hz, 18 H, H-4), 1.30 – 1.52 (m, 36 H, H-1/H-
2/H-3), 2.31 (s, 1 H, H-5), 6.09 – 7.15 (m, 8 H, H-Ph), 8.37
(s, 1 H, CH=N).
24.83 (d,
27.85 (d,
3
13
C{1H} NMR (CDCl3): δ = 13.77 (C4), 20.57 (C5),
JPC = 13.36 Hz, C3), 26.09 (d,
1
2
JPC = 11.62 Hz, C2),
JPC = 6.26 Hz, C1), 109.44 (C-Ph), 121.46 (C-Ph),
122.25 (C-Ph), 124.66 (C-Ph), 129.77 (C-Ph), 132.62 (C-Ph),
133.69 (C-Ph), 135.54 (C-Ph), 153.09 (C-Ph), 165.44 (C-Ph),
175.18 (C=N).
31
P{1H} NMR (CDCl3): δ = -9.6. TG: one steps;
Tbegin = 100 °C, Tend = 400 °C, ∆m = 83.36 %. DSC: Peak 1: T =
195 °C, ∆H1 = -5.56 J/g, Peak 2: T = 265 °C, ∆H2 = -15.32 J/g;
Peak 3: T = 338 °C, ∆H3 = 0.97 J/g.
123
Experimental Section
P(C1H2C2H2C3H2C4H3)3
O
Ag
C
H
N
P(C1H2C2H2C3H2C4H3)3
C5H3
Experimental Section
124
7.4 Crystal Refinement Data
-Complex 11c
Empirical formula
C22H42Ag2O18P4
Formula weight
934.18
Temperature
183(2) K
Wavelength
0.71073 Å
Crystal system
Triclinic
Space group
P-1
a
11.1620(5) Å
b
12.0909(6) Å
c
14.2526(7) Å
α
81.3930(10) °
β
82.2030(10) °
γ
72.9860(10) °
V
1810.01(15) Å3
Z
2
Density (calculated)
1.714 Mg/m3
Absorption coefficient
1.329 mm-1
F(000)
944
Crystal size
0.4 x 0.4 x 0.4 mm3
Theta range for data collection
1.77 to 26.02 °
Index ranges
-13 ≤ h ≤ 13, -14 ≤ k ≤ 14,
0 ≤ l ≤ 17
Reflections collected
11272
Independent reflections
7042 [R(int) = 0.0134]
Completeness to theta = 26.02°
98.6 %
Absorption correction
Empirical
Max. and min. transmission
0.99999 and 0.84142
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
7035 / 0 / 427
Goodness-of-fit on F2
1.066
Final R indices [I>2sigma(I)]
R1 = 0.0244, wR2 = 0.0613
R indices (all data)
R1 = 0.0274, wR2 = 0.0632
Largest diff. Peak and hole
0.764 and –0.626 e Å-3
Experimental Section
125
-Complex 21a
Empirical formula
C52H78Ag2N2O4P2
Formula weight
1072.84
Temperature
193(2) K
Wavelength
0.71073 Å
Crystal system
Ticlinic
Space group
P-1
a
8.6240(5) Å
b
11.9365(6) Å
c
13.8584(7) Å
α
66.6580(10)°
β
86.3260(10)°
γ
86.7490(10)°
V
1306.38(12) Å3
1
Z
Density (calculated)
Absorption coefficient
1.364 Mg/m3
0.854 mm-1
F(000)
560
Crystal size
0.4 x 0.2 x 0.2 mm3
1.60 to 26.38 °
Theta range for data collection
Index ranges
Reflections collected
-10 ≤ h ≤ 10, -13 ≤ k ≤ 14,
0 ≤ l ≤ 17
11389
Independent reflections
5320 [R(int) = 0.0415]
Completeness to theta = 26.38°
99.6 %
Absorption correction
Empirical
Max. and min. transmission
0.99999 and 0.72101
Refinement method
Data / restraints / parameters
Full-matrix least-squares on F2
5320 / 0 / 279
Goodness-of-fit on F2
1.051
Final R indices [I>2sigma(I)]
R1 = 0.0373, wR2 = 0.0789
R indices (all data)
R1 = 0.0531, wR2 = 0.0835
Largest diff. Peak and hole
0.504 and –0.619 e Å-3
Experimental Section
126
-Complex 21b
Empirical formula
C52H78Ag2N2O2P2
Formula weight
1040.84
Temperature
293(2) K
Wavelength
0.71073 Å
Crystal system
Triclinic
Space group
P-1
a
8.5906(15) Å
b
11.983(2) Å
c
13.727(2) Å
α
69.068(3)°
β
82.584(4)°
γ
85.165(3)°
V
1307.7(4) Å3
Z
1
Density (calculated)
1.322 Mg/m3
Absorption coefficient
0.848 mm-1
F(000)
544
Crystal size
0.4 x 0.2 x 0.1 mm3
Theta range for data collection
1.60 to 26.42 °
Index ranges
-10 ≤ h ≤1 0, -14 ≤ k ≤ 14,
-17 ≤ l ≤ 17
Reflections collected
9296
Independent reflections
5320 [R(int) = 0.0783]
Completeness to theta = 26.42°
97.4 %
Absorption correction
None
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
8853 / 0 / 280
Goodness-of-fit on F2
1.008
Final R indices [I>2sigma(I)]
R1 = 0.0658, wR2 = 0.1627
R indices (all data)
R1 = 0.0742, wR2 = 0.1667
Largest diff. Peak and hole
1.565 and –1.556 e Å-3
127
Summary
8 Summary
The purpose of this Ph.D. study was to synthesize new
silver(I) complexes and to investigate their suitability to be
used as CVD-precursors for the silver metallization.
Chapter
3
phosphites
contains
silver(I)
the
synthesis
complexes
of
of
phosphane
or
[(PnBu3)mAgX],
type:
[{P(OR)3}mAgX], [(nBu3P)mAgEAg(PnBu3)m] (m = 1, 2, 3; R = Me, Et;
X = carboxylate, E = dicarboxylate). The ratio between silver
and phosphane/phosphite ligands (Ag:P = 1:1; Ag:P = 1:2; Ag:P
=
1:3)
was
proved
1
by
H-NMR
spectroscopy,
while
the
coordination of the phosphane or phosphites to silver(I) was
demonstrated by
31
P{1H}-NMR spectroscopy. An exchange of the
phosphane and phosphite ligands was found and investigated by
low temperature
IR
31
P{1H} NMR spectroscopy.
spectroscopic
coordination
mode
metal
atom.
Mondentate,
were
found.
Also
of
study
the
X-ray
allows
carboxylic
chelate
and
to
units
determine
to
bridging
diffraction
analysis
a
the
transition
binding
reveal
modes
that
complex 11c [(P(OMe)3)2AgO2C(C4H3O)] has a dimeric structure in
the solid-state (Figure 1). The carboxylic unit is monodentate
bound to the silver atom.
R
C
O
P
O
Ag
Ag
P
P
O
P
O
C
R
Figure 1: Schematic view of the molecular structure of 11C
(R = C4H3O, P = P(OMe)3).
128
Summary
The
synthesized
carboxylates
and
phosphane
dicarboxylates
or
are
phosphite
either
silver(I)
solids
with
low
melting points or liquids. Most of these complexes (with two
and three phosphans or phosphites) are low viscous liquids,
which show good properties as CVD precursors. The stability of
these compounds increases with increasing coordination number.
In Chapter 4 the synthesis and the characterization of
phosphane
silver(I)
Schiff-base
complexes
of
type:
[(nBu3P)mAg{O-2-(C6H4)C(H)N(C6H4)-4-R}] (R = OMe, Me; m = 1, 2)
is illustrated. Monophosphane silver(I) Schiff-base complexes
are
solids,
while
diphosphane
silver(I)
Schiff-bases
are
viscous oils. Complexes 21a and 21b are dimeric in the solidstate.
N
P
CH
Ag
O
Ag
HC
N
O
P
Figure 2: Schematic view of the molecular structures of 21a
and 21b in the solid-state (P =
n
Bu3P).
The thermal behaviour of the above described complexes was
investigated
by
thermogravimetric
dalorimetric
studies.
depicted in Figure 3.
Examplary
and
the
differential
thermogram
of
scanning
7c
is
129
Weight %
Summary
100
80
60
40
20
0
∆ m = 8 0 .0 %
20
220
420
620
Temperature (°C)
Figure 3: TG trace of 7c (heating rate, 8 °C/min).
The volatility and the thermal stability of the phosphane
and phosphite silver(I) complexes were further investigated by
temperature-programmed
and
in-situ
time-of-flight
mass
spectrometry. The presence of silver-containing fragments was
used to indicate their volatility. The fragmentation path of
complex
10b
[(nBu3P)2AgO2CCH2Ph]
during
ionization
shows
a
similar behaviour, both by temperature programmed and in-situ
time-of-flight mass spectrometry. The following decomposition
mechanism can be formulated:
n
Bu3P
O
Ag
n
O
Bu3P
O
n
Bu3P
C CH2
Ag
+
O
m/z = 309
n
Bu3P
m/z = 202
The
mass
spectrometric
+
C CH2
Ag
m/z = 107
+
CO2
m/z = 44
investigations
Bu3P
m/z = 202
m/z = 136
+
n
CH2
m/z = 91
reveal
that
the
prepared phosphane silver(I) carboxylates are stable in the
gas
phase.
However,
the
respective
phosphane
silver
130
Summary
dicarboxylates are not volatile in the gas phase. Nevertheless
the
decomposition
of
these
species
offer
other
interesting
applications in, for example, spin coating, dip coating and
aerosol-assisted
CVD.
The
phosphane
Schiff-base
appear to be unstable in the gas phase and
complexes
are also not
suited to be used as precursors in silver CVD process.
Silver
films
were
deposited
by
starting
from
selected
phosphane silver(I) carboxylates as precursors. Also selected
phosphane silver(I) dicarboxylate species were tested for the
deposition of Ag. Deposition experiments were performed using
a
cold-wall
CVD
reactor
with
a
pulsed
spray
evaporation
system. Smooth and conductive silver coatings were obtained
with precursors 10b, 10d and 10e. The silver(I) dicarboxylate
complex 16b gives rise to rough and conductive silver films.
X-ray diffraction studies reveal that the deposited silver has
a cubic structure.
131
References
9 References
[1]
Handbook
of
the
Elements
(Ed:
G.
physicochemical
V.
Samsonov),
properties
IFI-Plenum,
of
the
New
York
1968.
[2]
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Report
Personal Data
139
Personal Data
Name
DJIELE NGAMENI, Patrice
Date and Place of birth 29.04.1973, Fondjomekwet (Cameroon)
Nationality
Cameroonian
Family Statut
Married with TONNANG Sountsa Judith since
27.12.2003
Languages
French, English, German
Education
Jun 1992
G.C.E Advanced Level in the Natur Science
and Mathematic at Government High School
of Bafia (Cameroon).
1992 – 2001
Studies in Chemistry at the
University of Yaounde I (Cameroon).
Jun 1998
Bachelor´s Degree in Chemistry.
Jul. 1999
Master´s Degree in Inorganic
Chemistry; specialisation in Analytical
Chemistry.
Sept. 2001
Master´s with Thesis (Diplôme des Etudes
Approfondies) dealing with
“Electrolytical treatment of wood: Means
of increasing the electrical conductivity
of Baillonella Toxisperma” under the
supervision of Prof. E. NGAMENI.
10.2001 – 06.2002
Begin a Ph.D. work on the
Topic: “Electrolytical treatment of wood”
with Prof. E. NGAMENI at the
University of Yaounde I (Cameroon).
Personal Data
07.2002 – Present
140
Ph.D. study at the Department of
Inorganic Chemistry, TU Chemnitz
(Germany) dealing with:
“Phosphane and Phosphite Silver(I)
Complexes: Synthesis, Reaction chemistry
And their Use as CVD precursors” under the
supervision of Prof. Dr. H. Lang.
Experience
07.2002 – Present
Assistent in Research and Practical at
the Department of Inorganic Chemistry, at
Chemnitz University of Technology
(Germany).
02.2004 – 03. 2004
Visit Ph. D. Student at the Department of
Physical Chemistry, University of Bielefeld
(Germany); research group of
Prof. Dr. Katharina KOHSE-HÖINGHAUS,
dealing with: “Deposition of silver
by pulsed spray CVD”.
10.1999 – 06.2002
Monitor in Physical Chemistry Practical
and Tutorial lessons at the Faculty of
Science, University of Yaounde I
(Cameroon).
Seminars
05-07.10.2003
Workshop Dingden (Germany)
DFG: CVD-Schwerpunkt Programm 1119
Poster: “Silver(I) carboxylates as CVD
Precursor”.
11.12.2003
Lecture at the University of Yaounde I
(Cameroon) on the topic: “Organo-silver(I)
complexes as precursors in the CVD process”.
141
Personal Data
02-04.06.2004
Workshop Pommersfeld (Germany)
DFG: CVD-Schwerpunkt Programm 1119
Poster: „ Untersuchungen des CVDAbscheidungsprozesses dünner Silberschichten“.
List of Publication
1- Thomas Haase, Katharina Kohse-Höinghaus, Naoufal Bahlawane, Patrice
Djiele, Heinrich Lang, Chem. Vap. Dep., 2004, in print.
2- Y. Shen, A. Jakob, P. Djiele, T. Haase, K. Kohse-Höinghaus, S.E.
Schulz, T. Gessner, and H. Lang, New J. Chemistry, 2004,
in
preparation.
- Further manuscripts are in preparation.
* Since Feb. 2003 Menber of the GDCh ( Gesselschaft Deutsch
Chemiker).
142
Acknowledgments
Acknowledgments
The present studies were carried out at the Institut of
Chemistry, Inorganic Chemistry Department, Chemnitz Technical
University (Germany), between 2002-2004.
I am particularly indebted to my supervisor Prof. Dr. H.
Lang
(Distinguished
support
and
Professor
constructive
Inorganic
Chemistry)
discussions,
which
for
his
enriched
my
knowledge and experience.
My
sincere
thanks
go
to
Dr.
Y.
Shen
for
his
close
cooperation in the laboratory as well as his invaluable help
and discussions.
Dr. B. Walfort is acknowledged for the X-ray structure
determination and for is fruitful discussions. Special thanks
go to Dr. T. Rüffer for his help and discussions in chemistry.
I
also
secretarial
appreciate
and
the
technical
friendly
staff
of
cooperation
our
of
Department.
the
I
am
thankful to all the menbers of Prof Lang´s group for their
cooperativeness and warm working atmosphere.
To Prof. Dr. Katharina Kohse-Höinghaus I give my deep
thanks
for
the
collaboration
in
mass
spectrometry
investigations and CVD experiments included in this work. I
would like to thank Dipl. Chem. T. Haase for his friendly help
during my stay in Bielefeld.
I owe special thanks to my friends Dr. B.P.T. Fokwa and
Dr. N. Bahlawane for reading this thesis as well as their
valuable suggestions.
Futhermore i whish to thank my wife Tonnang Sountsa Judith
for her love, patience and support throughout the study. I
also wish to express my warmest thanks to my parents, brothers
and sisters for their support and for encouraging me on the
road I had chosen.
The support of many friends troughout my research (Dr. C.
Nanseu, M.Sc. J.R. Fotsing, Dr. M.K. Fotsing) has also been
much appreciated.
Acknowledgments
143
And finally, I wish to express my sincere thanks to all,
who help me in preparing this thesis.
144
Selbständigkeitserklärung
Selbständigkeitserklärung
Hiermit
erkläre
ich,
dass
ich
die
vorliegende
Arbeit
selbständig und nur unter Verwendung der angegebenen Literatur
und Hilfsmitttel angefertigt habe.