Dithiocarbamate copper(I) and silver(I) complexes: Synthesis, structure and thermal behavior

Article abstract of DOI:10.1016/j.ica.2015.02.008

Complexes [M(PBu₃)_n(S₂CNRR′)] (M = Cu, Ag; n = 1, 2, 3; R = R′ = CH₂CHCH₂, (CH₂)₄, C₂H₄OH; R = Me, R′ = C₂H₄OH; R = Bu, R′ = C₂

Full text of DOI:10.1016/j.ica.2015.02.008

Inorganica Chimica Acta 429 (2015) 227–236
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Dithiocarbamate copper(I) and silver(I) complexes: Synthesis, structure
and thermal behavior
⇑
Robert Mothes, Holm Petzold, Alexander Jakob, Tobias Rüffer, Heinrich Lang
Technische Universität Chemnitz, Faculty of Natural Sciences, Institute of Chemistry, Inorganic Chemistry, 09107 Chemnitz, Germany
a r t i c l e i n f o
a b s t r a c t
0
0
Article history:
Complexes [M(PBu ) (S CNRR )] (M = Cu, Ag; n = 1, 2, 3; R = R = CH CH@CH , (CH ) , C H OH; R = Me,
3
n
2
0
2
2
2
4
2
4
Received 11 December 2014
Received in revised form 2 February 2015
Accepted 5 February 2015
0
R = C
2
H
4
OH; R = Bu, R = C
2
H
4
OH) (4–9) are accessible by the reaction of [Cu(PBu
)
3 n
Cl] (1a–c) or
0
[
[
Ag(PBu
Ag(PPh
3
)
n
(NO
(S
3
)] (2a–c) with [K(S
2
CNRR )] (3a–e). The respective silver(I) dithiocarbamates 7–9 and
0
3
)
2
2
CNRR )] (12a, R = Me; 12b, R = Bu) could be synthesized by the subsequent treatment of 3
] (10) giving [AgS
). Exemplary, the P{ H} NMR spectra of [Ag(PBu ) (S CNMe(C H OH)] (n = 1.0, 1.5, 2.0,
3 3 n 2 2 4
.5, 3.0, 3.5, 4.0, 4.5) were investigated in the temperature range of 308–178 K showing phosphine ligand
exchange processes in solution. The molecular structures of 12a,b in the solid state are reported confirm-
ing the monomeric architecture with coordination number 4 at silver, which is setup by a chelate-bonded
OH) unit and two coordinated PPh
samples was studied by thermogravimetry. Depending on R, R and the number of phosphines n, decom-
Available online 20 February 2015
0
with [AgNO
3
2
CNRR ] (11) followed by addition of n equivalents of the phosphine L
3
1
1
(L = PBu
3
, PPh
Keywords:
Metal
Metal sulfide
Dithiocarbamate
Dynamic NMR spectroscopy
Thermal decomposition
2
2
0
(j
-S,S ) S
2
CNR(C
2
H
4
3
ligands. The thermal behavior of selected
0
position occurs in varying temperature ranges giving different decomposition residues (Cu
Ag, Ag S), which were characterized by XRPD.
x
S, x = 1.96, 2;
2
Ó 2015 Elsevier B.V. All rights reserved.
1
. Introduction
Dithiocarbamate-containing coordination compounds repre-
Herein, we discuss the synthesis, properties, characterization,
and thermal behavior of a series of phosphine copper(I) and silver(I)
0
dithiocarbamate complexes of structural type [ML
n
(S
2
CNRR )]
0
sent a class of transition metal complexes, which are accessible
by using different synthetic methodologies [1]. Over the last dec-
ades, a versatile chemistry has been developed around them and
a wide-ranging field of applications including analytical chemistry
(M = Cu, Ag; L = PBu
3
, PPh
3
; n = 1, 2, 3; R = R = CH
2
CH@CH
2
, (CH
2
)
4
,
0
0
C
2
H
4
OH; R = Me, R = C
2
H
4
OH; R = Bu, R = C
2
H
4
OH).
[
[
2], material sciences [3], homogeneous catalysis [4], and biology
5] has been established. The enormous interest in dithiocarba-
2. Results and discussion
Phosphine copper(I) and silver(I) dithiocarbamate complexes of
mate compounds results from their ability to coordinate different
metals in diverse bonding modes [1,6], which, for example, allows
the simultaneous determination of copper and silver in waste-
water [7]. For all applications, consolidated knowledge of the coor-
dinating behavior of the respective dithiocarbamates complexes is
of prime importance. Though, with exclusion of limited examples,
the interaction between copper(I) and/or silver(I) dithiocarba-
mates and phosphines regarding spectroscopic and structural
features is only rarely described in literature [8]. Hence, we got
interested in the investigation of the interaction between selected
0
0
type [M(PBu
CH@CH , (CH
3
)
n
(S
2
CNRR )] (M = Cu, Ag; n = 1, 2, 3; R = R = CH
H OH; R = Me, R = C H OH; R = Bu, R = C H
2 4 2 4 2
2
0
0
2
2
)
4
, C
4
OH) (4–9) have been prepared by reacting [Cu(PBu
3
)
n
Cl] (1a–c)
0
or [Ag(PBu
3
)
n
(NO
3
)] (2a–c) with [K(S
2
CNRR )] (3a–e) as shown in
Scheme 1 (Table 1). The potassium dithiocarbamate salts 3a–e
were accessible by treatment of the secondary amines dially-
lamine, pyrrolidine, diethanolamine, 2-(methylamino)ethanol, or
2-(butylamino)ethanol with an excess of carbon disulfide in
ethanolic potassium hydroxide solutions at 0 °C [9]. Another
synthetic methodology to prepare the phosphine silver(I) dithio-
copper(I) and silver(I) dithiocarbamates with phosphines PR
R = Bu, Ph) and their use as precursors in deposition processes.
3
(
carbamates 7–9 and additional [Ag(PPh
R = Me; 12b, R = Bu) relates upon the subsequent reaction of 3d,e
with stoichiometric amounts of [AgNO ] (10) to afford [AgS
CNR(C OH)] (11a, R = Me; 11b, R = Bu) followed by addition of
n equivalents of the phosphine PR (n = 1, 2, 3) (Scheme 1)
3 2 2 2 4
) (S CNR(C H OH)] (12a,
3
2
2 4
H
⇑
Corresponding author.
3
http://dx.doi.org/10.1016/j.ica.2015.02.008
020-1693/Ó 2015 Elsevier B.V. All rights reserved.
0

2
28
R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
(
i) K[S CNRR'] (3a-e)
2
[
M(PBu ) X]
[M(PBu ) S CNRR']
3 n 2
3
n
-
KX
1
a-c, 2a-c
4 - 9
M = Cu, X = Cl : 1a, n = 1
M = Cu : 4, n = 1
5, n = 2
3
3
3
a, R = R' = CH CH=CH
2
2
1
b, n = 2
c, n = 3
M = Ag, X = NO : 2a, n = 1
b, R, R' = (CH )
2
4
1
6, n = 3
c, R = R' = C H OH
2
4
M = Ag : 7, n = 1
8, n = 2
3
3d, R = Me, R' = C H OH
2
4
2
b, n = 2
3
e, R = Bu, R' = C H OH
2 4
2
c, n = 3
9, n = 3
(
ii) [AgNO ] (10)
(iii)/(iv) n L
3
K[S CNRR']
[Ag(S CNRR')]
[AgL (S CNRR')]
n 2
2
2
3
11a, b
L = PBu 7 - 9, n = 1 - 3
3
,
L = PPh 12, n = 2
3,
1
1
2a, R = Me, R' = C H OH
2 4
2b, R = Bu, R' = C H OH
2
4
Scheme 1. Synthesis of 4–9, 11 and 12 (Table 1). ((i) pentane, 0 °C; (ii) acetonitrile/ethanol (ratio 1:50, v/v), 0 °C; (iii) L = PBu
5 °C).
3
, pentane, 0 °C; (iv) L = PPh
3
, dichloromethane,
2
Table 1
The IR spectra of 4–9, 11 and 12 are characterized by distinct
0
n 2
Complexes [ML (S CNRR )] (4–9, 11 and 12).
absorptions typical for the dithiocarbamate units with vibrations
ꢀ1
ꢀ1
0
(m
~
(mC–S) (Section 4) [1].
~
Compd.
M
L
n
R
R
Yield [%]a
at ca. 1500 cm
C–N) and 1000 cm
Generally, the Bonati and Ugo [10] criterion based on the number
~
and splitting of mC–S bands at 1050–950 cm is used for the differ-
4
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Cu
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
Ag
PBu
PBu
PBu
PBu
PBu
PBu
PBu
PBu
PBu
PBu
PBu
PBu
PBu
3
3
3
3
3
3
3
3
3
3
3
3
3
1
2
2
2
3
3
3
3
1
2
2
3
3
C
C
C
CH
C
C
CH
(CH
C
C
CH
C
2
2
2
H
H
H
4
4
4
OH
OH
OH
Me
Me
93
94
91
87
93
90
86
88
92
91
88
92
ꢀ1
5
5
5
6
6
6
6
7
8
8
9
9
1
1
1
1
a
b
c
a
b
c
C
2
H
4
OH
CH@CH
entiation of chelating and monodentate binding modes of dithio-
carbamates. More lately, Kellner et al. [11] proposed interligand
coupling of the CS ligand as origin of the splitting and hence ruled
out the possibility of predicting the dithiocarbamate binding motif
from IR vibrations. Nevertheless, the presence of solely one CS
band indicates a chelating binding type as also discussed in the
dynamic NMR section and the solid state structure (see below).
As expected, the hydroxyl functionality gives rise to a broad
2
CH@CH
2
CH
Me
2
2
2
H
H
4
OH
OH
2
4
2 4
C H OH
2
CH@CH
2
CH
2
CH@CH
2
d
2 4
)
b
2
H
H
4
OH
OH
Me
Me
b
a
b
a
b
1a
1b
2a
2b
2
4
b
2
CH@CH
OH
CH@CH
2
CH
Me
2
CH@CH
2
2
b
2
H
4
b
ꢀ1
CH
2
2
CH
Me
Bu
2
CH@CH
86
96
89
93
band at 3350 cm . All vibrations proposed for the phosphine
c
C
C
C
C
2
H
2
H
2
H
2
H
4
OH
4
OH
4
OH
4
OH
ligand, if present in the respective compound, were found, being
only slightly shifted with respect to those of the free donors
(Section 4).
c
d
PPh
PPh
3
3
2
2
Me
Bu
d
96
1H NMR spectroscopy allows the assignment of all organic
a
b
c
Based on charged 1a–c or 2a–c.
Reaction pathway (i).
Based on charged 3.
groups present (Section 4). As exemplary shown for [Ag(PBu
3 2
)
(S CNMe(C OH))] (8a) (Fig. 1), upon decreasing the temperature
2
2 4
H
d
the resonance signals for the dithiocarbamate functionality are
slightly shifted to higher field. The signal corresponding to the
OH proton is most affected and shifted to lower field, which is like-
ly caused by the formation of stronger hydrogen-bonds [12].
In addition, C{ H} NMR spectroscopy can be used for monitor-
ing the progress of the formation of 4–9, 11 and 12 starting from 3,
which is accompanied by a distinctive shift of the resonance
signals of the quaternary dithiocarbamate carbon atoms to higher
field (3a–e, 214.5–208.0 ppm; 4–9, 11 and 12, 213.0–203.7 ppm)
(Section 4). The data are in agreement with similar dithiocarba-
mate transition metal complexes [8a].
Based on charged 11.
(
Section 4). After appropriate work-up, the PPh
were obtained as solids, while the respective PBu
3
-based compounds
-functionalized
1
3
1
3
transition metal complexes are liquids. Further conspicuous is that
the appropriate pale yellow copper(I) complexes are sensitive to
air- and moisture, while the off-white silver(I) derivatives are
stable under similar conditions, however, upon exposure to light
they decompose in between days forming elemental silver. The
tri-n-butylphosphine metal complexes 4–9 are soluble in most
common polar and non-polar organic solvents, while the PPh
ligands in 12a,b are responsible for the less solubility of these
complexes (Section 4).
3
The coordination of the phosphine ligands to copper(I) or
silver(I) in dithiocarbamates 4–9 and 12 can best be monitored
3
1
1
by P{ H} NMR spectroscopy, since the respective chemical shift
gives evidence of the bonding behavior between the phosphorus
and the transition metal atom (Section 4) [13]. Additional evidence
Complexes 4–9, 11 and 12 were characterized by elemental
1
13
1
31
1
analysis, IR and NMR ( H,
C{ H},
P{ H}) spectroscopy
1
07 31
Ag
109
31
Ag
(
Section 4). The thermal behavior of selected samples was studied
comes from the J
and J
P
coupling constants of the appro-
P
by TG (=Thermogravimetry). The molecular structures of 12a,b in
the solid state are reported.
priate silver(I) species (Fig. 2). Furthermore, with increasing num-
ber of phosphine ligands at silver following trends were observed:

R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
229
respectively) [14d]. As expected, the analogous copper complexes
show no coupling pattern under similar conditions. The additional
signal broadening for the phosphine copper(I) species (up to
9
000 Hz) results from the quadrupole effect of the copper isotopes
Cu and Cu (I = 3/2), respectively, which makes the appropriate
6
3
65
studies in comparison to silver more complicated [15].
3
1
1
The temperature dependent P{ H} NMR spectra of representa-
tive [Ag(PBu (S CNMe(C OH))] (8a) are shown in Fig. 2.
3
)
2
2
2 4
H
The broad singlet observed for 8a at ꢀ9.6 ppm (298 K, not
3
1
1
depicted) in the P{ H} NMR spectra starts broadening by lower-
ing the temperature resulting in a broad doublet between 223
and 213 K (coalescence temperature, T
93 K (Fig. 2). It is well known that in NMR spectroscopy variable
temperature lead to a shift of the resonance signals [14a,16]. This
phenomenon is also found for [Ag(PBu (S CNMe(C OH))] (8a)
298 K, ꢀ9.6 ppm; 183 K, ꢀ10.2 ppm). At 183 K the signals are
c
), which sharpens until
1
3
)
2
2
2 4
H
(
sharp enough to allow the extraction of the two coupling constants
Fig.
Ag(PBu
83–243 K).
1. Cutout
of
temperature
OH))] (8a) in D
2
dependent
-dichloromethane (temperature range:
1H
NMR
spectra
of
107
31
109
31
J
Ag
P
P
= 380 Hz and J Ag = 440 Hz (Fig. 2). This finding is also in
[
1
)
3 2
2
(S CNMe(C
2
H
4
agreement with phosphine silver(I) carboxylates of general type
AgL (O CR)]/[AgL ][O CR] (L = phosphine, phosphite; n = 1, 2, 3;
R = single bonded organic group) [14], i.e. [Ag(PBu (O CMe)]/
Ag(PBu ][O CMe] [14a].
To further investigate complex [Ag(PBu
the influence of the number n (n = 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0,
[
n
2
4
2
3
)
n
2
(
(
i) the 107Ag–31P and 107Ag–31P coupling constants decreases and
ii) the resonance signals appear at higher field (Section 4). A typi-
[
3
)
4
2
3 n 2 2 4
) (S CNMe(C H OH))],
cal observation for the silver(I) complexes is the loss of coupling at
ambient temperature indicating a fast exchange of the phosphine
ligands L on the NMR time scale. This was reported for various
3
1
1
4
.5) of the PBu
troscopy at 183 K (Fig. 3, top). Subsequent addition of free phos-
phine PBu CNMe(C OH))]
(d = ꢀ32.3 ppm) [17] to [Ag(S
resulted in well-resolved and separated signals for three distinct
3
ligands was investigated by P{ H} NMR spec-
2 4
H
copper(I) and silver(I) species of general type [ML
n
4
Y]/[ML ][Y]
3
2
(
L = phosphine, phosphite; M = Cu, Ag; n = 1, 2, 3; Y = organic or
species ([Ag(PBu
3
)(S
2
CNMe(C
2
H
4
OH))] (7): ꢀ3.9 ppm; [Ag(PBu
3
)
2
inorganic group) [13,14]. In order to obtain well-resolved silver–
phosphorus coupling patterns the interchange of ligands has to
be decelerated. Indeed, low-temperature 31P{ H} NMR spectra
show the typical two superimposed doublets. The intensity ratio
between the two doublets reflects the natural abundance of the
(
S
2
CNMe(C
2
H
4
OH))] (8a): ꢀ10.2 ppm; [Ag(PBu
3
)
4
][(S CNMe(C H
2
2
4
1
OH))]: ꢀ19.2 ppm) (Fig. 3, Section 4). While in 7 the phosphine
3
1
1
ligand gives rise to a signal at ꢀ3.9 ppm in the P{ H} NMR spec-
trum, the further coordination of a PBu ligand to silver led to a
3
two silver isotopes (both isotopes 1 Ag and
07
109
Ag have a nuclear
spin I = 1/2 and have a natural abundance of 52% and 48%,
resonance signal at higher field. This is in accordance with the con-
cept that the Lewis acidity of silver(I) decreases resulting in a less
deshielding of the phosphors atom. Furthermore, JAgP were largest
1
07
31
in the mono-phosphine silver(I) complex
P
7 (J Ag = 549 Hz,
1
09
31
J
Ag P
= 634 Hz) and becomes smallest in the tetrakis(phosphine)
107 31 109 31
species [Ag(PBu
2
3
)
4
][(S
2
CNMe(C
2
H
4
109
OH))] (J Ag
P
P
= 219 Hz, J Ag =
107
31
31
P P
52 Hz) via 8a (J Ag = 380 Hz, J Ag = 440 Hz) (Fig. 3, top), which
can be explained by the weakening of the Ag–P bond with increasing
numbers of PBu at silver and a lower 5s(Ag) character of the Ag–P
bond. The trend in the coupling constants is very similar to the
3
silver(I) carboxylate system of type [Ag(PBu
CMe] previously reported [14a].
In contrast to similar carboxylate systems [14], [AgL
CNMe(C
with n ꢁ 3 (Fig. 3, top), where two species are visible. The first spe-
cies (ꢀ10.3 ppm) can be assigned to [AgL (S CNMe(C OH))] as it
appears as the only system in the spectra with n ꢁ 2. The second
ꢀ19.2 ppm) is [AgL ][S CNMe(C OH)], which is an accordance
coordination complexes, i.e. [Ag(PBu ][O CMe]
14a]. Obviously the dithiocarbamate ligand strongly prefers a
3 n
) (O
2
CMe)]/[Ag(PBu
3 4
) ]
[O
2
3
(S
2
2
4
H OH))] was not observed. This is best seen for the spectra
2
2
2 4
H
(
4
2
2 4
H
+
to other [AgL
4
]
3
)
4
2
[
j
2
0
-S,S coordination mode [1], as found in the solid state structure
analogue 12a (vide infra, X-ray structure and [18]).
Therefore, the expected complex [AgL (S CNMe(C OH))], which
for the PPh
3
3
2
2 4
H
requires a monodentate binding mode of the dithiocarbamate, is
destabilized and hence not observed.
The bis(phosphine) adduct [AgL (S CNMe(C H OH))] is the pre-
2 2 2 4
ferred species within this system. This can be concluded from the
spectra with n ꢁ 2, since only very small (less than 5%) additional
signals ([AgL(S
2
CNMe(C
2
H
4
OH))], ꢀ3.9 ppm; [AgL
4
][S
CNMe(C
CNMe(C
OH)] (n = 1, 2) does not reflect the statistical distribu-
tion. This shows that a disproportionation of three equivalents
2
CNMe(C
H
2 4
2
H
4
OH)],
OH))] appear.
OH))]/[AgL ][S
ꢀ
19.2 ppm) to the main species [AgL
Clearly, this distribution of [AgL (S
CNMe(C
2
(S
2
n
2
2
H
4
4
2
Fig. 2. Temperature-dependent 31P{ H} NMR spectra of 8a in D
1
2 4
H
2
-dichloromethane
(
temperature range: 183–243 K).

2
30
R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
Fig. 3. a) 31P{ H} NMR spectra of complexes resulting from [AgS
1
CNMe(C
H
OH)] (11a) and n equivalents of PBu
(n ꢁ 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5) in D
2
2
4
3
2
-
⁄
sec
à
dichloromethane at 183 K. ( free PBu
2
3
Bu, always present as trace in PBu . Please, notice that this may have an influence on the line widths and the signal positions; for
n ꢁ 1 some precipitation afforded 11a along with higher concentration of [AgL
2
S
2
CNMe(C
2
H
4
OH)]; #for n ꢁ 4.5 a broad signal of free L at ꢀ32 ppm arises). b) Combination of
three 31P{ H} EXSY NMR spectra of [Ag(PBu
1
CNMe(C
3 n
) S
2
2
H
4
OH)] (n ꢁ 1.5, 2.5, 4.5) in D
2
-dichloromethane at 183 K (0.4, 0.2, 0.4 s mixing time, respectively). (Cross peaks have
1
2
3
#
been assigned to the three reaction r , r and r , the lower indices give the reaction direction (f = forward, b = backward). ( for n ꢁ 4.5 additional signals of free L arise at
ꢀ
32 ppm.).
[
[
AgL
2
(S
][S
2
CNMe(C
2
H
4
OH))] to two [AgL(S
OH)] is disfavored. In spectra with n > 4 a broad
was observed.
In order to gain a deeper insight into the exchange mechanism
2
CNMe(C
2
H
4
OH))] and one
NMR spectrum reveals the presence of a 2:0.3:0.6 mixture of
0
0
AgL
4
2
CNMe(C
2
H
4
[AgLL (S
CNMe(C
2 2 4 2 2 4 2 2
CNMe(C H OH)], [AgL (S CNMe(C H OH)] and [AgL (S
2
3
1
1
singlet corresponding to free PBu
3
2
H
4
OH)], respectively (Eq. (1)). The P{ H} NMR signals
0
corresponding to L are located at ca. 25 ppm, while signals for L
of the phosphines, 3 P{ H} EXSY NMR spectra were recorded
(
1
1
(PBu
) were found around ꢀ12 ppm (Fig. 4, top). As discussed
3
c
Fig. 3, bottom). These spectra show the expected cross peaks for
above, the more electron-donating ligand P Hex
3
let arise the
a stepwise phosphine exchange.
new signal at higher field. Nevertheless, the coupling constants
107 31 109 31
To further prove the identity and phosphine silver ratio n espe-
J
Ag
P
P
(360–400 Hz) and J Ag (420–460 Hz) fall in the typical
0
cially for [AgL
2
(S CNMe(C H
2 2 4
OH)] a mixed complex [AgLL (S
2
range of bis(phosphine) adducts [14a,17] (vide supra). The two sig-
0
CNMe(C
2
H
4
OH)] was prepared by adding one equivalent of
nals assigned to [AgLL (S
2
CNMe(C
2
H
4
OH)] allow extraction of the
c
0
2
P Hex
3
(L ) to a solution of [Ag(PBu
3
)(S
2
CNMe(C
2
H
4
OH))] (7) in
phosphorous–phosphorous coupling constant ( JPP = 110 Hz), and
the coupling pattern agrees to a 1:1 ratio between L and L in
0
D
2
-dichloromethane as depicted in Eq. (1). The formation of
0
31
1
31 31
1
0
[
AgLL (S
2
CNMe(C
2
4
H OH)] was monitored by P{ H}, P, P{ H}
[AgLL (S
2 2
CNMe(C H
4
OH)]. The coupling pathways are further illus-
3
1
1
31
1
31
31
1
COSY and P{ H} EXSY NMR spectroscopy (Fig. 4). The P{ H}
trated by the P– P{ H} COSY NMR spectrum shown in Fig. 4

R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
231
3
1
1
c
Fig. 4. Top: P{ H} NMR spectra of complexes resulting from [Ag(PBu
)(S
3 2
2
CNMe(C H
4
OH))] (7) and one equivalent of P Hex
3
in D
2
-dichloromethane at 183 K. Bottom, left:
31
31
1
c
31
31
1
c
P– P{ H} COSY NMR spectrum of 7 and P Hex
3
in D
2
-dichloromethane at 183 K. Bottom, right: P– P{ H} EXSY NMR spectrum of 7 and P Hex
3
in D
2
-dichloromethane at
2
13 K (0.2 s mixing time).
bottom left). The 31P–31P{ H} EXSY NMR spectrum presents the
1
(
Table 2
Selected bond distances [Å] and angles [°] for 12a,b a.
expected cross peaks proving phosphine exchange between all three
species. In summary, this allows undoubtedly the determination of
12a
12b
the silver ligand ratios n in the system [AgL
AgL ][S CNMe(C OH)] (n = 1, 2).
n
(S
2
CNMe(C
2
H
4
OH)]/
Bond distances
Ag1–S1
Ag1–S2
Ag1–P1
Ag1–P2
C1–S1
[
4
2
2 4
H
2.6592(9)
2.6380(9)
2.4964(9)
2.4172(8)
1.720(4)
1.732(4)
1.333(5)
Ag1–S1
Ag1–S2
Ag1–P1
Ag1–P2
C1–S1
2.6090(10)
2.6717(10)
2.4255(10)
2.4658(10)
1.714(4)
L'
[AgLY]
[AgLL'Y]
2 2
0.5 [AgL Y] + 0.5 [AgL' Y]
7
7 + L'
8a
ð1Þ
C1–S2
C1–N1
C1–S2
C1–N1
1.727(4)
1.341(5)
c
L = PBu3, L' = P Hex Y = S CNMe(C H OH)
3,
2
2
4
Bond angles
P1–Ag1–P2
P1–Ag1–S1
P1–Ag1–S2
P2–Ag1–S1
P2–Ag1–S2
S1–Ag1–S2
Ag1–S1–C1
Ag1–S2–C1
S1–C1–S2
122.53(3)
95.01(3)
108.10(3)
131.93(3)
118.11(3)
68.35(3)
83.29(13)
84.16(12)
119.1(2)
120.3(3)
120.6(3)
P1–Ag1–P2
P1–Ag1–S1
P1–Ag1–S2
P2–Ag1–S1
P2–Ag1–S2
S1–Ag1–S2
Ag1–S1–C1
Ag1–S2–C1
S1–C1–S2
123.52(3)
125.31(3)
114.54(3)
103.12(3)
108.66(3)
68.48(3)
85.74(15)
83.54(14)
119.4(2)
120.3(3)
120.2(3)
The molecular structures of [Ag(PPh
3
)
2
(S
2
CNMe(C
2
H
4
OH))]
(
12a) and [Ag(PPh (S CNBu(C H OH))] (12b) in the solid state
3
)
2
2
2 4
were established by single X-ray structure analysis. Single crystals
could be grown from slow diffusion of diethyl ether into a saturat-
ed solution containing 12a or 12b in dichloromethane at ambient
temperature. Complexes 12a,b crystallize in the triclinic space
ꢀ
group P1. The bond lengths of both complexes differ up to 3%
N1–C1–S1
N1–C1–S2
N1–C1–S1
N1–C1–S2
and corresponding bond angles up to 8%. Selected bond distances
(
Å) and angles (°) are summarized in Table 2. For important crystal
a
data, collection and refinement parameters see Section 4. The
molecular structures of 12a,b are illustrated in Fig. 5.
The estimated standard deviation(s) of the last significant digits are shown in
parentheses.
Both complexes are monomeric revealing a chelating
j
2-S,S0
binding mode of the dithiocarbamate ligand, which is by far the
angles of 12a,b correlate with those values found for similar com-
most common structural motif. [1] The Ag(I) ion possesses a some-
3 2 2 2 4
plexes, i.e. [Ag(PPh ) (S CN(CH ) ))] [18].
what distorted tetrahedral AgP
setup by two datively-bonded PPh
dithiocarbamate group (Fig. 5). The bond distances and bond
2
S
2
coordination environment,
ligands and one chelated
TG (=Thermogravimetry) studies of selected samples were car-
ried out to gain first information on the thermal behavior of the
respective dithiocarbamate copper(I) and silver(I) complexes in
3

2
32
R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
Fig. 5. ORTEP diagrams (50% probability level) of 12a (left) and 12b (right). For disordered atoms only one set is shown. All hydrogen atoms, except for the O-bonded
hydrogen atoms, are omitted for clarity.
Cu-Kα1
1
00
80
60
40
20
0
6a
1
00
6
a
5a
6a
Cu1.96S (P43212)
6
b
8
0
0
0
0
6
c
6
d
6
4
2
0
100
200
300
400
500
100
200
300
400
20
30
40
50
60
70
Temperature [°C]
Temperature [°C]
2Θ [°]
, flow rate 60 mL min 1, heating rate 10 K minꢀ1) of 6a–d. Middle: TG traces (N
ꢀ
, flow rate 60 mL min , heating rate 10 K min ) of 5a and 6a. Right:
ꢀ1
ꢀ1
Fig. 6. Left: TG traces (N
XRPD pattern of the TG residue of 6d showing peaks for Cu1.96S [tetr. chalcocite, JCPDS 29-0578].
2
2
Cu-Kα1
1
00
9a
9b
9
9
a
b
Ag S (P21/n)
8
0
0
0
0
2
Ag(Fm-3m)
6
4
2
0
100
200
300
400
500
20
30
40
50
60
70
Tempera tt ure [°C]
2Θ[°]
, flow rate 60 mL min 1, heating rate 10 K minꢀ1) of 9a and 9b. Right: XRPD pattern of the TG residue of 9a and 9b showing peaks for Ag [JCPDS 04-
ꢀ
Fig. 7. Left: TG traces (N
783] and -Ag S [acanthite, JCPDS 14-0072].
2
0
a
2
the solid state. The appropriate TG traces are shown in Figs. 6 and 7.
These Figures also include the XRPD pattern of the TG residues
obtained. The studies were conducted at atmospheric pressure
compared with 6c,d (ca. 250 °C). Fig. 6 also shows that complexes
6a–d decompose in a one-step (6a) or two-step (6b–d) process
with mass losses between 88.0 and 90.3% (Table 3). The difference
between the observed and the calculated values for 6c,d are with
2.5 and 1.5% higher than those ones for 6a,b, correlating well with
ꢀ1
under a nitrogen purge (60 mL min ) with a constant heating
ꢀ1
rate of 10 K min . Thermal decomposition characteristics are
summarized in Table 3.
2
theoretical percentages calculated for Cu S. The higher deviation
From Fig. 6 it can be seen that the decomposition of complexes
for 6c,d is most probably attributed to carbon impurities. The
respective TG residues were analyzed by XRPD studies (6a:
Fig. 6, right). In these studies it was found that only the residues
6
a–d starts at ca. 75 °C and is completed depending on the nature
of the dithiocarbamate ligand between 270 and 480 °C, whereby
a,b show with 210 °C the lowest onset temperatures, when
6
x
obtained from 6a,b show crystalline Cu S (6a,b: tetr. chalcocite

R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
233
0
Table 3
complexes of type [M(PBu
)
(S
, C
CNRR )] (M = Cu, Ag; n = 1, 2, 3;
3
n
2
Thermal decomposition characteristics of 5, 6, and 9.
0
0
R = R = CH
2
CH@CH
2
2
, (CH )
4
2
H
4
1
OH; R = Me, R = C
H
2 4
OH; R = Bu,
(S
OH)] (n = 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5) and
31
#
i
–#
m [%])
f
[°C]
0
[°C]
o
m/m
[%]
0
x
[%]
M2S
x
[%]
M
m/
XRPDa
R = C
0
2
H
4
OH) are described. P{ H} NMR studies of [Ag(PBu
3
)
n
2
(
D
m
0
ꢀ
x
M2S
CNMe(C
H
2
4
[%]
c
[
Ag(PBu )(P Hex )(S CNMe(C H OH))] in the temperature range
3 3 2 2 4
5
5
5
6
6
6
6
9
9
a
b
c
90–290
87.2)
90–300
87.2)
90–600
85.9)
70–270
90.3)
75–380
90.2)
75–480
88.0)
75–450
88.7)
55–270
86.6)
60–520
84.9)
216
221
255
210
211
240
247
197
232
12.8
12.8
14.1
9.7
12.9
12.3
12.5
9.7
ꢀ0.1
0.5
Cu1.96
S
of 308–178 K prove phosphine ligand exchange processes in solu-
tion. 2D NMR Experiments allowed the determination of the silver
(
Cu1.96
-b
S
ligand ratios n in the system [AgL
CNMe(C OH)] (n = 1, 2) and reveal the bis(phosphine) adduct
[AgL (S CNMe(C OH))] as preferred species. Single X-ray struc-
ture analysis verify the monomeric structures of [Ag(PPh (S
CNR(C OH))] (R = Me, Bu) in the solid state. Dithiocarbamate
CNR(C
n 2 2 4 4 2
(S CNMe(C H OH)]/[AgL ][S
(
2
H
4
1.6
(
2
2
2 4
H
a
b
c
0.0
Cu1.96
S
S
3
)
2
2
(
2
H
4
9.8
9.4
0.4
2
Cu S,
2
0
S
2
2 4
H OH) is thereby chelate-bonded j -S,S to the silver
(
Cu1.96
b
12.0
11.3
13.4
15.1
9.5
2.5
-
atom. Thermogravimetric studies were carried out for selected
samples. By varying the substituents at the dithiocarbamate nitro-
gen atom a decreasing of the onset temperatures for the decompo-
(
d
a
b
9.8
1.5
-b
(
sition was achieved. The respective decomposition residues (Cu
x = 1.96, 2; Ag, Ag S) were characterized by XRPD. Due to their
thermal properties, especially complexes [M(PBu (S CNMe(C
OH)] (M = Cu, Ag) are excellent candidates for the deposition
x
S,
14.3
14.0
12.9
12.2
ꢀ0.9
1.1
Ag S/Ag
2
(
2
Ag
3
)
2
2
2
(
H
4
of copper- and silver-sulfides using different deposition techniques
including CVD (=Chemical Vapor Deposition) and spin-coating
processes. This single source precursor (=SSP) approach allows
the formation of thin layers for potential applications in solar
selective coatings and IR detectors which can be generated much
more safe then common methods using hazardous sulfur sources.
#
i
: Initial decomposition temperature. #
Onset temperature. : Mass fraction. M2S: Metal sulfide content, calcd. residue for
solely formation of M S. : Metal content, calcd. residue for solely formation of M.
f o
: Final decomposition temperature. # :
x
2
x
x
M
a
Crystalline parts of TG residue analyzed by XRPD.
No crystalline properties.
b
with x = 1.96; 6b: b-chalcocite with x = 2). This discrepancy
between 6a,b and 6c,d from the TG as well as the XRPD experi-
ments can likely be explained by the proposed decomposition
mechanism of (b-hydroxyethyl)-methyldithiocarbamates as
recently published by Nomura et al. [19] and our group [20]
4
. Experimental
4.1. General
3
(Scheme 2). The influence of the number n of the PBu ligands pre-
All reactions were carried out under an argon or nitrogen atmo-
sent in the complex on the thermal induced decomposition is
shown in Fig. 6 (middle). It was found that the higher the number
n, the lower the initial decomposition temperature is, which is an
accordance to other phosphine metal(I) carboxylate complexes
sphere using standard Schlenk techniques. Hexane and pentane
were purified by distillation from sodium/benzophenone ketyl;
acetonitrile and dichloromethane from calcium hydride and
ethanol from sodium and diethylphthalate. The NMR solvents were
dried over molecular sieve and were stored under argon
atmosphere.
[
21].
The thermal behavior of phosphine silver(I) dithiocarbamates
a,b is compared in Fig. 7 (left) and shows initial temperatures of
9
around 60 °C. While the one-step decomposition of 9a is finished
at ca. 270 °C, allyl-functionalized 9b undergoes a multi-step
decomposition, which is completed at ca. 500 °C. Both compounds
reveal a discrepancy between found TG residue values (9a, 13.4%;
4
.2. Instruments
FT-IR spectra were recorded with a Thermo Nicolet IR 200 spec-
trometer. NMR spectra were recorded with a Bruker Avance III 500
9
b, 15.1%) and the residue calculated for the solely formation of
1
13
1
spectrometer (500.3 MHz for H, 125.7 MHz for
C{ H} and
02.5 MHz for P{ H}). Chemical shifts are reported in d (parts
per million) units downfield from tetramethylsilane (d = 0.0) with
Ag S (9a, 14.3%; 9b, 14.0%) (Table 3). Interestingly, in case of 9b
2
31
1
2
XRPD measurements of the respective TG residues (Fig. 7, right)
display solely silver as crystalline material, while for 9a majorly
1
the solvent as reference signal ( H NMR: CDCl
3
, d = 7.26; CD
2
Cl
, d = 2.50. C{ H} NMR: CDCl
d = 54.00; CD OD, d = 49.00; DMSO-d
d = 39.52. P{ H} NMR: standard external rel. 85% H PO
, d = 139.0.). P{ H} NMR spectra were recorded under
conditions of broad band proton decoupling in CDCl or CD Cl
For low temperature experiments CD Cl solutions (0.6 mL) of
2
3
6
,
,
,
crystalline
The in Scheme
b-hydroxyethyl)-methyldithiocarbamates might be responsible
for these findings.
a-Ag
2
S (acanthite) along with traces of silver is found.
13
1
d = 5.32; CD
3
OD, d = 3.31, DMSO-d
Cl
6
2
proposed decomposition mechanism of
d = 77.16; CD
2
2
,
3
(
31
1
3
4
, d = 0.0;
31
1
P(OMe)
3
3
2
2
.
3
. Conclusion
Straightforward synthetic methodologies for the preparation of
2
2
the respective complex (0.1 mmol) were prepared. Temperatures
were varied by passing either pre-cooled or pre-heated dry nitro-
gen over the sample, and 5 min were allowed for equilibration.
a series of phosphine dithiocarbamate copper(I) and silver(I)
S
S
x 2
(
Bu
3
P)
n
M
S
N
M S
HO
N
M
S
M2S
H
- H S
2
S
-
n Bu3P
HO
-
O
N
M = Cu, Ag; n = 1, 2, 3
Scheme 2. Proposed decomposition mechanism of (b-hydroxyethyl)-methyl-functionalized dithiocarbamates.

2
34
R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
The melting points were determined using a Gallenkamp MFB 595
10 M melting point apparatus. Microanalyses were performed
with a C, H, N analyzer FlashAE 1112 instrument (Thermo
Company). TG experiments were performed with Mettler
Toledo TGA/DSC1 1100 system with an UMX1 balance. Powder
X-ray diffraction patterns of all samples were obtained with a
4.3.2.2.
[Cu(PBu
3
)
2
(S
2
CNMe(C
2
H
4
OH))]
(5a). Yield:
580 mg
0
(0.94 mmol, 94% based on 1b). Anal. Calc. for C28
(618.42): C, 54.38; H, 10.11; N, 2.26. Found: C, 54.10; H, 10.03;
N, 2.20% IR (NaCl): 3398 (O–H); 2956, 2928, 2871 (C–H); 1464
H62CuNOP S
2 2
a
ꢀ
1
1
3
(C–N); 1096 (C–S) cm
.
H NMR (CDCl
J
3
): d 4.15 (t,
H,H = 5 Hz, NCH CH OH, 2H), 3.41 (s,
, 3H), 3.09 (t, JH,H = 5 Hz, OH, 1H), 1.53–1.49 (m, PCH (CH
CH CH CH , 12H), 1.38–1.31 (m,
H,H = 7 Hz, P(CH CH 18H).
): d 211.1 (s, S CN), 61.8 (s, NCH CH OH),
OH), 41.4 (s, NCH ), 26.9 (s, PCH (CH CH ),
CH CH ), 24.8 (s, P(CH CH CH
): d ꢀ18.7.
JH,H = 5 Hz,
3
NCH
NCH
2
CH
2
OH, 2H), 3.88 (q,
2
2
3
STOE-STADI-P diffractometer using Cu
K
a
radiation (40 kV,
3
2
2 2
)
4
0 mA) and a Ge(111)-monochromator.
CH
3
, 12H), 1.46–1.40 (m, PCH
CH CH 12H), 0.87 (t,
C{ H} NMR (CDCl
6.3 (s, NCH CH
5.6 (s, PCH
2
2
2
3
3
P(CH
2
)
2
2
3
,
J
2
)
3
3
,
1
3
1
3
2
2
2
4.3. Reagents
5
2
2
2
3
2
)
2 2
3
2
CH
2
2
3
2
)
2
2
3
), 13.9 (s,
Complexes [Cu(PBu
3
)
n
0
Cl] and [Ag(PBu
3
)
n
(NO
, (CH
OH), [Ag(S CN(CH
OH))] and [Ag(S CNBu(C OH))] [20] were
3
)] [22] (n = 1, 2, 3),
3
1
1
P(CH
2
)
3
CH
3
). P{ H} NMR (CDCl
3
0
K[S
R = C
2
CNRR ] [9,20] (R = R = CH
2
CH@CH
2
2
)
4
, C H
2 4
OH; R = Me,
)], [23]
0
0
2
4
H OH; R = Bu, R = C
2
H
4
2
CH@CH )
2 2 2
[
Ag(S
2
CNMe(C
2
H
4
2
2
H
4
4.3.2.3.
(0.91 mmol, 91% based on 1b). Anal. Calc. for C29
(648.45): C, 53.71; H, 9.95; N, 2.16. Found: C, 53.33; H, 9.88; N,
.16%. IR (NaCl): 3406 (O–H); 2956, 2927, 2869 (C–H); 1463
[Cu(PBu
3
)
2
(S
2
2
CN(C H
4
OH)
2
)]
(5b). Yield:
590 mg
prepared by published procedures. All other chemicals were
purchased by commercial suppliers and were used as received.
2 2 2
H64CuNO P S
2
ꢀ
1
1
3
(
C–N); 1100 (C–S) cm
.
H NMR (CDCl
3
): d 4.16 (t,
JH,H = 5 Hz,
4
.3.1. Synthesis of [K(S
According to reference [9], 3e was prepared as follows: Amine
NHBu(C OH) (12.30 g, 105 mmol) was added to an ethanolic
solution (500 mL) of KOH (5.60 g, 100 mmol) at 0 °C. Afterwards,
an ethanolic solution (100 mL) of CS (6.0 mL, 15.3 g, 200 mmol)
2 2 4
CNBu(C H OH))] (3e)
NCH
2
CH
2
OH, 4H), 3.95 (bs, NCH
2
CH
36H), 0.88 (t,
): d 212.5 (s, S
OH), 27.0 (s, PCH (CH
), 24.9 (s, P(CH CH CH ), 13.9 (s,
): d ꢀ19.0.
2
OH, 4H), 3.41 (s, OH, 2H),
3
1
.47–1.33 (m, PCH
2
CH CH CH
2
2
3
,
J
H,H = 7 Hz,
CN), 61.8
CH ),
2 4
H
1
3
1
P(CH
2
)
3
CH
CH
5.7 (s, PCH
3
, 18H). C{ H} NMR (CDCl
3
2
(
s, NCH
2
2
OH), 55.9 (s, NCH CH
2
2
2
2
)
2
3
2
2
2
CH
2
CH
2
CH
3
2
)
2
2
3
was added dropwise. After stirring for 5 h at ambient temperature,
the reaction mixture was concentrated under reduced pressure
and dry diethyl ether was added until precipitation reached com-
pletion. Subsequently, 3e was filtered, washed with diethyl ether
3
1
1
2
P(CH )
3
CH
3
). P{ H} NMR (CDCl
3
4.3.2.4. [Cu(PBu
(0.87 mmol, 87% based on 1b). Anal. Calc. for C31
(640.47): C, 58.13; H, 10.07; N, 2.19. Found: C, 58.43; H, 9.99; N,
2.05%. IR (NaCl): 3390 (O–H); 2955, 2925, 2874 (C–H); 1463
3
)
2
(S
2
2
CN(CH CH@CH
)
2 2
)] (5c). Yield: 560 mg
64CuNP
(
3 ꢂ 50 mL) and dried in oil pump vacuum. Compound 3e was
obtained as a colorless solid, soluble in ethanol and methanol.
Yield: 21.97 g (95 mmol, 95% based on NHBu(C OH)). Mp
(231.42): C, 36.33; H, 6.10; N,
.05. Found: C, 36.00; H, 6.07; N, 5.93%. IR (KBr): 3325 (O–H);
H
2 2
S
2
H
4
ꢀ1
1
1
6
2
24 °C. Anal. Calc. for C
7
H
14KNOS
2
(C–N); 1096 (C–S) cm
.
3
H NMR (CDCl ): d 5.88–5.81 (m,
J
3
3
3
NCH
2
CHCH
2
, 2H), 5.11 (ddd,
, 4H), 4.53 (d, 3JH,H = 6 Hz, NCH
CH CH , 36H), 1.38–1.31 (m, P(CH
H,H = 7 Hz, P(CH
): d 210.7 (s, S CN), 133.0 (s, NCH
CHCH ), 53.4 (s, NCH CHCH ), 27.0 (s, PCH
25.7 (s, PCH ), 24.9 (s, P(CH CH CH
): d ꢀ18.5.
H,H = 6 Hz,
J
H,H = 6 Hz,
CHCH , 4H), 1.50–
CH CH
C{ H} NMR
), 116.9 (s,
(CH CH ),
), 14.0 (s,
JH,H = 6 Hz,
ꢀ
1 1
943, 2924, 2864 (C–H); 1458 (C–N); 1108 (C–S) cm
OD): 4.79 (s, OH, 1H), 4.22 (t, 3
HH = 6 Hz, NCH CH
.14–4.08 (m, NCH (CH CH 2H), 3.89 (t,
CH OH, 2H), 1.77–1.71 (m, NCH CH CH CH , 2H), 1.38–1.30
m, N(CH CH CH HH = 7 Hz, N(CH CH , 3H).
, 2H), 0.95 (t, 3
C{ H} NMR (CD OD): 213.6 (s, S CN), 61.2 (s, NCH CH OH),
6.5/56.2 (s/s, NCH CH OH/NCH (CH CH ), 30.0 (s, NCH CH
CH CH ), 21.1 (s, N(CH CH CH ), 14.3 (s, N(CH CH ). HRMS (ESI-
TOF, neg. mode) [MꢀK] , m/z Calcd.: 192.0511, Found: 192.0515.
.
H NMR
NCH
2
CHCH
2
2
2
(
CD
3
J
2
2
OH, 2H),
1.40 (m, P(CH
18H), 0.87 (t,
(CDCl
NCH
2
)
2
2
3
2
1
)
2
2
3
,
3
3
13
4
NCH
2
2
)
2
3
,
JHH = 6 Hz,
J
2
)
3
CH
3
,
27H).
CHCH
2
2
2
2
2
2
3
3
2
2
(
2
)
2
2
3
J
2
)
3
3
2
2
2
2
2
2
)
2
3
1
3
1
3
2
2
2
2
CH
2
CH
2
CH
3
2
)
2
2
3
3
1
1
5
2
2
2
2
)
2
3
2
2
2
P(CH )
3
CH
3
). P{ H} NMR (CDCl
3
2
3
2
)
2
2
3
2
)
3
3
ꢀ
4.3.2.5.
[Cu(PBu
3
)
3
(S
2
CNMe(C
H
2 4
OH))]
(6a). Yield:
760 mg
(
0.93 mmol, 93% based on 1c). Anal. Calc. for C40
H89CuNOP S
3 2
4
.3.2. Synthesis of Tri-n-butylphosphine copper(I) and silver(I)
dithiocarbamates (4–9)
Complex [Cu(PBu
(820.74): C, 58.54; H, 10.93; N, 1.71. Found: C, 58.16; H, 10.95;
N, 1.62%. IR (NaCl): 3369 (O–H); 2950, 2862 (C–H); 1462 (C–N);
ꢀ
1
1
3
3
)
n
Cl] (1a–c) (1.0 mmol) or [Ag(PBu
3
)
n
3
(NO )]
1098 (C–S) cm
NCH CH OH, 2H), 3.89–3.86 (m, NCH
3H), 3.09 (t,
54H), 0.87 (t, 3JH,H = 7 Hz, P(CH
(CDCl ): 211.2 (s, CN), 61.8 (s, NCH
(s, NCH OH), 41.3 (s, NCH ), 27.3 (s, PCH (CH
PCH CH C,P = 10 Hz, P(CH
s, P(CH ). P{ H} NMR (CDCl
): d ꢀ20.8.
.
H
NMR (CDCl
3
):
CH
2 3
H,H = 5 Hz, OH, 1H), 1.46–1.32 (m, P(CH )
d
4.15 (t,
OH, 2H), 3.41 (s, NCH
CH
JH,H = 5 Hz,
(2a–c) (1.0 mmol) was dissolved in pentane (50 mL) and
2
2
2
2
3
,
,
0
3
K[S
0
1
2
CNRR ] (3a–e) (1.0 mmol) was added in a single portion at
J
3
13
1
°C. After stirring this suspension at ambient temperature for
0 h, filtration through a pad of Celite and evaporation of all vola-
2
)
3
CH
3
,
27H).
C{ H} NMR
CH OH), 56.2
CH ), 26.1 (s,
CH CH ), 13.9
3
d
S
2
2
2
tiles in oil-pump vacuum gave the title complexes as pale yellow
Cu) or off-white (Ag) liquids.
2
CH
CH
CH
2
3
2
2
)
2
3
3
(
2
2
2
CH
3
), 24.8 (d,
J
2
)
2
2
3
3
1
1
(
2
)
3
3
3
4
(
(
.3.2.1.
0.93 mmol, 93% based on 1a). Anal. Calc. for C16
416.10): C, 46.18; H, 8.48; N, 3.37. Found: C, 46.31; H, 8.55; N,
[Cu(PBu
3
)(S
2
CNMe(C
2
H
4
OH))]
(4). Yield:
390 mg
H
35CuNOPS
2
4.3.2.6.
3 3
[Cu(PBu ) (S
2
CN(C
H
2 4
2
OH) )]
(6b). Yield:
765 mg
(0.90 mmol, 90% based on 1c). Anal. Calc. for C41H91CuNO P S
2 3 2
3
.29%. IR (NaCl): 3388 (O–H); 2955, 2928, 2871 (C–H); 1463 (C–
(850.76): C, 57.88; H, 10.78; N, 1.65. Found: C, 57.66; H, 10.60;
N, 1.53%. IR (NaCl): 3393 (O–H); 2950, 2924, 2870 (C–H); 1468
ꢀ1
1
): d 4.15 (t, 3
OH, 2H), 3.41 (s, NCH
CH CH CH
, 9H). C{ H} NMR (CDCl
OH), 56.3 (s, NCH CH OH),
), 25.4 (s, PCH CH CH CH ),
P{ H} NMR
N); 1098 (C–S) cm
NCH
3
1
d 211.0 (s, S
4
2
.
H NMR (CDCl
CH
H,H = 5 Hz, OH, 1H), 1.58–1.34 (m, PCH
3
J
H,H = 5 Hz,
ꢀ
1
1
3
2
CH
H), 3.09 (t,
8H), 0.89 (t, 3JH,H = 7 Hz, P(CH
2
OH, 2H), 3.88–3.85 (m, NCH
2
2
3
,
,
(C–N); 1098 (C–S) cm
NCH CH OH, 4H), 3.95 (bs, NCH
1.47–1.33 (m, P(CH CH , 54H), 0.88 (t,
C{ H} NMR (CDCl ): 212.5 (s,
OH), 55.9 (s, NCH CH OH), 27.4 (s, PCH
CH CH CH
), 24.8 (d, 3JC,P = 9 Hz, P(CH
CH
.
H NMR (CDCl
3
): d 4.16 (t, JH,H = 5 Hz,
3
J
2
2
2
3
2
2
2
CH OH, 4H), 3.41 (s, OH, 2H),
2
13
1
3
2
)
3
CH
CH
CH
3
3
):
2
)
3
3
J
H,H = 7 Hz, P(CH
CN), 61.3 (s,
(CH CH ), 26.1
CH CH ), 13.9 (s,
2 3 3
) CH ,
1
3
1
2
CN), 61.8 (s, NCH
), 26.5 (s, PCH
2
2
2
2
27H).
NCH CH
(s, PCH
P(CH
3
d
S
2
1.3 (s, NCH
3
2
(CH
2
)
2
3
2
2
2
3
2
2
2
2
2
2
)
2
3
3
1
1
4.8 (s, P(CH
2
)
2
CH
2
CH
3
), 13.9 (s, P(CH
2
)
3 3
CH ).
2
2
2
1
3
2
)
2
2
3
3
1
(
CDCl
3
): d ꢀ16.9.
2
)
3
3
). P{ H} NMR (CDCl
3
): d ꢀ20.3.

R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
235
4
(
(
.3.2.7. [Cu(PBu
0.92 mmol, 92% based on 1c). Anal. Calc. for C43
842.79): C, 61.28; H, 10.88; N, 1.66. Found: C, 60.81; H, 10.95;
3
)
3
(S
2
CN(CH
2
CH@CH
2
)
2
)] (6c). Yield: 775 mg
PCH
P(CH
2
CH
2
CH
2
CH
3
), 24.7 (d, 3JC,P = 13 Hz, P(CH
2
)
2
CH
2 3
CH ), 13.9 (s,
3
1
1
H
91CuNP
3
S
2
2
)
3
CH
3
). P{ H} NMR (CDCl
3
): d ꢀ9.9.
N, 1.60%. IR (NaCl): 3360 (O–H); 2960, 2869 (C–H); 1464 (C–N);
4.3.2.12.
[Ag(PBu
3
)
3
(S
2
CNMe(C
2
H
4
OH))]
(9a). Yield:
795 mg
ꢀ1 1
1
2
4
095 (C–S) cm
H), 5.11 (ddd,
H), 4.53 (d,
.
H NMR (CDCl
H,H = 6 Hz, 3 H,H = 6 Hz, 3
H,H = 6 Hz, NCH CHCH
, 36H), 1.38–1.31 (m, P(CH
3
): d 5.88–5.81 (m, NCH
2
CHCH
CHCH
2
,
,
(0.92 mmol, 92% based on 2c). Anal. Calc. for C40H89AgNOP S
(865.06): C, 55.54; H, 10.37; N, 1.62. Found: C, 55.48; H, 10.30;
N, 1.53%. IR (NaCl): 3384 (O–H); 2957, 2928, 2871 (C–H); 1465
(C–N); 1099 (C–S) cm . H NMR (CDCl
3 2
3
J
J
JH,H = 6 Hz, NCH
2
2
3
J
2
2
,
4H), 1.50–1.40 (m,
CH CH , 18H), 0.87
, 27H). C{ H} NMR (CDCl ): d 210.7
CHCH ), 116.7 (s, NCH CHCH ), 53.2 (s,
), 27.3 (s, PCH (CH CH ), 26.1 (s, PCH CH CH CH ),
C,P = 7 Hz, P(CH CH CH ), 13.9 (s, P(CH CH
NMR (CDCl
): d ꢀ20.1.
ꢀ
1 1
): d 4.27 (t, 3
P(CH
2
)
2
CH
H,H = 7 Hz, P(CH
CN), 133.0 (s, NCH
CHCH
2
CH
3
2
)
2
2
3
3
3
J
H,H = 5 Hz,
OH, 2H), 3.92 (dd, JH,H = 10 Hz, JH,H = 5 Hz, NCH CH OH,
, 3H), 1.52–1.34 (m,
3
13
1
3
(
t,
J
2
)
3
CH
3
3
NCH
2
CH
2
2
2
3
(
s, S
2
2
2
2
2
2H), 3.58 (t, JH,H = 5 Hz, OH, 1H), 3.50 (s, NCH
3
3
NCH
5.8 (d,
2
2
2
2
)
2
3
2
2
2
3
PCH
2
CH
2
CH
2
CH
3
, 54H), 0.90 (t,
): d 213.2 (s, S
OH), 43.0 (s, NCH
J
H,H = 7 Hz, P(CH
2
)
3
CH
3
, 27H).
CH OH),
C,P = 8 Hz,
), 24.7 (d,
3
31
1
13
1
2
J
2
)
2
2
3
2
)
3
3
). P{ H}
C{ H} NMR (CDCl
3
2
CN), 62.3 (s, NCH
2
2
1
3
57.8 (s, NCH
PCH (CH CH
C,P = 12 Hz, P(CH
(CDCl
): d ꢀ17.7.
2
CH
), 26.4 (d,
CH CH
2
3
), 27.9 (d,
J
2
2
2
)
2
3
J
C,P = 2 Hz, PCH
2
CH
2
CH
2
CH
3
3
31
1
4
8
6
.3.2.8. [Cu(PBu (S CN(CH
8% based on 1c). Anal. Calc. for C41
0.29; H, 10.98; N, 1.71. Found: C, 60.30; H, 11.20; N, 1.60%. IR
3
)
3
2
2
)
4
)] (6d). Yield: 720 mg (0.88 mmol,
89CuNP (816.75): C,
J
2
)
2
2
3
), 14.0 (s, P(CH
2
)
3
CH ). P{ H} NMR
3
H
S
3 2
3
(
cm
NaCl): 3378 (O–H); 2960, 2870 (C–H); 1458 (C–N); 1096 (C–S)
4.3.2.13. [Ag(PBu
(0.86 mmol, 86% based on 2c). Anal. Calc. for C43
(887.11): C, 58.22; H, 10.34; N, 1.58. Found: C, 57.84; H, 10.19;
N, 1.57%. IR (NaCl): 3393 (O–H); 2954, 2931, 2872 (C–H); 1464
3
)
3
(S
2
CN(CH
2
CH@CH
2
)
2
)] (9b). Yield: 590 mg
91AgNP
ꢀ1
1
3
3
4
.
H NMR (CDCl
3
): d 3.68 (t,
J
H,H = 7 Hz, C H
/N(CH 4H), 1.43–1.27 (m,
H,H = 7 Hz, P(CH
2
,C H
2
/N(CH
2
)
4
,
H
3 2
S
2
5
4
H), 1.90–1.85 (m, C H
P(CH CH
, 54H), 0.83 (t, 3
NMR (CDCl ): d 205.2 (s, S
PCH (CH )CH
4.7 (d,
2
,C H
2
2
)
4
,
13
1
2
)
3
3
J
2
)
3
CH
3
, 27H). C{ H}
2
5
ꢀ1
1
3
2
CN), 51.3 (s, C ,C /N(CH ), 27.2 (s,
2
)
4
(C–N); 1095 (C–S) cm
NCH CHCH , 2H), 5.07 (dd,
4H), 4.59 (d,
.
H NMR (CDCl
J
3
): d 5.90–5.83 (m,
H,H = 9 Hz, NCH CHCH
4H), 1.50–1.30 (m,
H,H = 7 Hz, P(CH CH , 27H).
): d 212.4 (s, S CN), 133.2 (s, NCH CHCH ),
), 54.7 (s, NCH CHCH C,P = 8 Hz,
), 27.6 (d, 1
C,P = 4 Hz, PCH CH CH CH ), 24.5 (d,
), 13.8 (s, P(CH CH
3
4
3
3
2
2
3
), 26.1 (s, C ,C /N(CH
C,P = 10 Hz, P(CH CH
P{ H} NMR (CDCl
): d ꢀ22.3.
2
)
4
), 26.0 (s, PCH
2
CH
2
CH
2
CH
CH
3
),
).
2
2
H,H = 8 Hz,
J
2
2
,
3
3
2
J
2
)
2
2
CH ), 13.8 (s, P(CH
3
2
)
3
3
J
H,H = 5 Hz, NCH CHCH ,
2
2
3
1
1
3
3
PCH
2
CH
2
CH
2
CH
3
, 54H), 0.85 (t,
J
2
)
3
3
1
3
1
C{ H} NMR (CDCl
3
2
2
2
4
9
7
.3.2.9. [Ag(PBu
2% based on 2a). Anal. Calc. for C16
.66; N, 3.04. Found: C, 41.27; H, 7.60; N, 2.82%. IR (NaCl): 3390 (O–
3 2
)(S CNMe(C
2 4
H OH))] (7). Yield: 425 mg (0.92 mmol,
116.3 (s, NCH
PCH (CH CH
C,P = 13 Hz, P(CH
(CDCl
): d ꢀ15.9.
2
CHCH
), 26.1 (d,
CH CH
2
2
2
J
2
H
35AgNOPS (460.43): C, 41.74; H,
2
2
2
)
2
3
J
2
2
2
3
3
31
1
J
2
)
2
2
3
2
)
3
3
). P{ H} NMR
ꢀ1
1
H); 2925, 2870 (C–H); 1463 (C–N); 1099 (C–S) cm
.
H NMR
3
3
(
CDCl
3
):
d
4.24 (t,
J
HH = 5 Hz, NCH
CH OH, 2H), 3.49 (s, NCH
bs, OH, 1H), 1.57–1.33 (m, PCH (CH CH 18H), 0.90 (t,
, 9H). C{ H} NMR (CDCl ): d 212.9 (s,
CH OH), 58.2 (s, NCH CH OH), 43.4 (s, NCH ),
CH ), 25.9 (d, JP–C = 8 Hz, PCH CH CH CH ), 24.7
d, JP–C = 12 Hz, P(CH CH CH ), 13.9 (s, P(CH CH ). P{ H} NMR
CDCl
): d ꢀ6.3.
2
CH
2
OH, 2H), 3.94 (dd,
3
HH = 9 Hz, 3JHH = 7 Hz, NCH
J
2
2
3
, 3H), 3.40
4.3.3. Synthesis of bis(triphenylphosphine) silver(I) dithiocarbamates
12a,b
(
2
)
2 2
3
,
3
13
1
J
HH = 7 Hz, P(CH
CN), 62.0 (s, NCH
7.6 (s, PCH (CH
2
)
3
CH
3
3
Complex [AgS
2 2 4
CNR(C H OH)] (11a, R = Me; 11b, R = Bu)
S
2
(
(
2
2
2
2
2
3
(1.0 mmol) was suspended in dichloromethane (50 mL) and PPh
3
2
2
2
)
2
3
2
2
2
3
(2.0 mmol) was added in a single portion. After stirring this sus-
pension at ambient temperature for 4 h, filtration through a pad
of Celite and evaporation of the solvent in oil-pump vacuum gave
3
31
1
2
)
2
2
3
2
)
3
3
3
1
2a,b as off-white solids.
4.3.2.10.
3 2
[Ag(PBu ) (S
2 2
CNMe(C H
4
OH))]
(8a). Yield:
605 mg
(
(
2
0.91 mmol, 91% based on 2b). Anal. Calc. for C28
662.74): C, 50.74; H, 9.43; N, 2.11. Found: C, 50.30; H, 9.38; N,
.02%. IR (NaCl): 3371 (O–H); 2955, 2928, 2870 (C–H); 1463
H
62AgNOP
2
S
2
4.3.3.1.
(0.93 mmol, 93% based on 11a). Mp: 170 °C. Anal. Calc. for C40
AgNOP (782.68): C, 61.38; H, 4.89; N, 1.79. Found: C, 61.03; H,
4.99; N, 1.67%. IR (KBr): 3400 (O–H); 3069, 3055, 3015, 3000,
[Ag(PPh
3
)
2
S
2
CNMe(C
2
H
4
OH)]
(12a). Yield:
730 mg
H
38
2 2
S
ꢀ1 1
): d 4.25 (t, 3
(
C–N); 1097 (C–S) cm
.
H NMR (CDCl
3
J
HH = 5 Hz,
HH = 5 Hz, 3JHH = 5 Hz,
, 3H), 3.37 (bs, OH, 1H), 1.60–1.56
, 12H), 1.52–1.44 (m, PCH CH CH CH , 12H),
.42–1.35 (m, P(CH CH CH 12H), 0.90 (t, HH = 7 Hz,
, 18H). C{ H} NMR (CDCl ): d 213.0 (s, S CN), 62.1
CH OH), 58.1 (s, NCH CH OH), 43.3 (s, NCH ), 27.7 (d,
P–C = 6 Hz, PCH (CH CH ),
), 24.7 (d,
3
ꢀ1 1
NCH
NCH
2
CH
CH
2
OH, 2H), 3.93 (p.q (dt),
OH, 2H), 3.51 (s, NCH
(CH CH
J
2964, 2924, 2859 (C–H); 1479 (C–N); 1094 (C–S) cm
(CDCl ): 7.34–7.29 (m, C , 12H), 7.28–7.24 (m, C
7.22–7.17 (m, C , 12H), 4.11 (t,
HH = 6 Hz, CH CH OH, 2H), 3.44 (s, NCH
): d signal for S CN not found, 134.4 (d, JCP = 15 Hz,
.
H NMR
, 6H),
2 2
CH OH, 2H),
2
2
3
3
6
H
5
6 5
H
3
(
m, PCH
2
2
)
2
3
2
2
2
3
H
6 5
J
HH = 5 Hz, NCH
, 3H). C{ H}
3
3
13
1
1
P(CH
2
)
2
2
3
,
J
3.87 (p.q,
J
2
2
3
1
3
1
2
3
) CH
3
3
2
NMR (CDCl
3
2
i
2
o
p
(
s, NCH
2
2
2
2
3
C /C
128.7 (d,
NCH CH OH), 44.3(s, NCH
6
H
5
), 134.0 (d,
J
CP = 17 Hz, C /C
6
H
5
), 129.7 (C /C
), 61.5 (s, NCH CH OH), 58.5 (s,
). P{ H} NMR (CDCl ): d 4.8.
6 5
H ),
1
2
3
m
J
2
2
)
2
3
26.0
P–C = 13 Hz, P(CH
). P{ H} NMR (CDCl
): d ꢀ9.6.
(d,
J
P–C = 10 Hz,
CH ), 13.9
JCP = 9 Hz, C /C
6
H
5
2
2
3
31
1
PCH
(
2
CH
2
CH
2
CH
3
J
2
)
2
CH
2
3
2
2
3
3
3
1
1
s, P(CH
)
2 3
CH
3
3
4
.3.3.2.
(0.96 mmol, 96% based on 11b). Mp: 161 °C. Anal. Calc. for C43
AgNOP (824.76): C, 62.62; H, 5.38; N, 1.70. Found: C, 62.13; H,
5.32; N, 1.75%. IR (KBr): 3388 (O–H); 3067, 3057, 3013, 3002,
[Ag(PPh
3
)
2
S
2
CNBu(C
2
H
4
OH)]
(12b). Yield:
790 mg
4
3 2
.3.2.11. [Ag(PBu ) (S
2
CN(CH
2
CH@CH
2
2
) )] (8b). Yield: 603 mg
H
44
(
(
1
0.88 mmol, 88% based on 2b). Anal. Calc. for C31
H
64AgNP
684.79): C, 54.37; H, 9.42; N, 2.05. Found: C, 54.34; H, 9.60; N,
.91%. IR (NaCl): 3392 (O–H); 2959, 2930, 2871 (C–H); 1464
2
S
2
2 2
S
ꢀ
1 1
2953, 2928, 2867 (C–H); 1481 (C–N); 1111 (C–S) cm
(CDCl ): d 7.42–7.38 (m, C , 12H), 7.37–7.33 (m, C
7.31–7.27 (m, C , 12H), 4.17 (t,
H), 4.01–3.97 (m, NCH CH OH/CH
HH = 5.7 Hz, OH, 1H), 1.79–1.73 (m, CH
.
H NMR
, 6H),
OH, 2
4H), 2.92 (t,
CH , 2H), 1.36–
, 2H), 0.92 (t, JHH = 7.4 Hz, CH CH CH CH
): d 211.2 (s, S CN), 134.4 (d, JCP = 15 Hz,
ꢀ
1
1
(
C–N); 1095 (C–S) cm
.
H NMR (CDCl
3
): d 5.94–5.87 (m,
H,H = 11 Hz, NCH CHCH
4H), 1.60–1.55 (m,
12H), 1.52–1.45 (m, PCH CH CH CH 12H),
.42–1.36 (m, PCH CH CH CH 12H), 0.89 (t, H,H = 7 Hz,
, 18H). C{ H} NMR (CDCl ): d 212.5 (s, S CN), 133.1
CHCH ), 116.8 (s, NCH CHCH ), 55.2 (s, NCH CHCH ),
C,P = 6 Hz, PCH (CH CH ), 26.1 (d, C,P = 10 Hz,
3
6
H
5
6 5
H
CH
2 2
, 2H), 5.13 (dd, 3JH,H = 4 Hz, 3
J
,
H
3
J
HH = 5.4 Hz, NCH
(CH CH
CH CH
NCH
4
PCH CH CH CH
1
P(CH
(
2
2
CHCH
H), 4.63 (d,
2
2
2
6
5
3
J
H,H = 5 Hz, NCH
2
CHCH
2
,
2
2
2
2
)
2
3
,
3
2
2
2
3
,
2
2
2
3
,
J
2
2
2
3
3
3
2
2
2
3
,
J
1.28 (m, CH
3H). C{ H} NMR (CDCl
C /C
(d,
2
CH
2
CH
2
CH
3
2
2
2
3
,
1
3
1
13
1
2
3
) CH
3
3
2
3
2
i
2
o
p
s, NCH
7.7 (d,
2
2
2
2
2
2
6
3
H
5
), 134.1 (d,
J
CP = 17 Hz, C /C
6 5 6 5
H ), 129.7 (C /C H ), 128.8
1
2
m
J
2
2
)
2
3
J
J
CP = 9 Hz, C /C
6
H
5
), 61.5 (s, NCH
2
CH OH), 56.4/56.1 (s/s,
2

2
36
R. Mothes et al. / Inorganica Chimica Acta 429 (2015) 227–236
NCH
N(CH
2
CH
2
OH/NCH
2
(CH
2
)
2
CH
3
), 29.2 (s, NCH
2
CH
2
CH
2
CH
3
), 20.3 (s,
): d 4.9.
Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary
data associated with this article can be found, in the online version,
at http://dx.doi.org/10.1016/j.ica.2015.02.008.
31
1
)
2 2
CH
2
CH ), 14.0 (s, N(CH
3
2
)
3
CH
3
). P{ H} NMR (CDCl
3
4
.3.4. Single crystal X-ray diffraction analysis
Single crystals of 12a,b suitable for X-ray diffraction analysis
References
were obtained by diffusion of diethyl ether into a saturated
dichloromethane solution containing the respective compound.
Data were collected with an Oxford Gemini S diffractometer at
[
1] G. Hogarth, Transition Metal Dithiocarbamates: 1978–2003, in Progress in
Inorganic Chemistry, Volume 53 (Ed. K. D. Karlin), 2005, John Wiley & Sons Inc,
Hoboken, NJ, USA and references cited therein.
[
2] (a) A.A. Ensafi, S. Abbasi, Anal. Sci. 16 (2000) 377;
1
17 (12a) and 100 K (12b) using Cu Ka radiation (k = 1.54184 Å).
(
(
b) M.K. Deb, S. Chakravarty, R.K. Mishra, J. Indian Chem. Soc. 73 (1996) 551;
c) M. Sperling, X.F. Yin, B. Welz, Analyst 117 (1992) 629;
The structures were solved solved by direct methods and refined
2
by full-matrix least-squares procedures on F . [24] All non-hydro-
(d) A.K. Malik, A.L.J. Rao, J. Chin. Chem. Soc. 39 (1992) 235.
3] (a) H.S. Sangari, G.S. Sodhi, J. Kaur, Thermochim. Acta 171 (1990) 49;
[
[
gen atoms were refined anisotropically, and a riding model was
employed in the treatment of the hydrogen atom positions.
(
(
b) P. O’Brien, J.H. Park, J. Waters, Thin Solid Films 431 (2003) 502;
c) R. Nomura, H. Matsuda, Trends Inorg. Chem. 2 (1991) 79;
1
2b: The OH group and the additional solvent molecule CH
2
Cl
2
(d) C. Bernal, E.A. Neves, E.T.G. Cavalhiero, Thermochim. Acta 370 (2001) 49;
e) M. Kemmler, M. Lazell, P. O’Brien, D.J. Otway, J.H. Park, J.R. Walsh, J. Mater.
(
are disordered and have been refined to split occupancies of 0.52/
Sci. Mater. Electron. 13 (2002) 531.
4] (a) Z.-Q. Wang, S.-W. Lu, H.-F. Guo, N.-H. Hu, Polyhedron 11 (1992) 1131;
0
.48 (O1, C8, Cl1, Cl2).
(
b) A. Srivastava, Y.A. Ma, R. Pankayatselvan, W. Dinges, K.M. Nicholas, J. Chem.
Soc., Chem. Commun. 853 (1992) 42.
[5] (a) R. Ramesh, K. Natarajan, Synth. React. Inorg. Met. Org. Chem. 26 (1996)
677;
4
.3.4.2. Crystal data for 12aꢃCH
2
Cl
2
. C41
H
40AgCl
2
NOP
2
S
2
,
M =
ꢀ1
ꢀ
867.57 g mol , T = 117 K, k = 1.54184 Å, triclinic, P1, a = 12.2750(7) Å,
1
b = 13.0674(7) Å, c = 13.9428(9) Å,
c
8
a
= 98.401(5)°, b = 93.825(5)°,
(b) D.G. Craciunescu, C. Molina, A. Doadrio-López, E. Parrondo-Iglesias, A.
Gomez, M. Sanchez de Leon, L. Fernandez de Simon, E. Gastón de Iriarte, C.
Guirvu, An. R. Acad. Farm 53 (1987) 205.
3
ꢀ3
= 116.357(6)°, V = 1960.5(2) Å ,
qcalc = 1.470 g cm
, F(000) =
88, crystal dimensions 0.36 ꢂ 0.18 ꢂ 0.14 mm, Z = 2, minimum/
[
6] G. Exarchos, S.D. Robinson, J.W. Steed, Polyhedron 20 (2001) 2951.
ꢀ1
maximum transmission: 1.00000/0.66015,
l
= 7.403 mm
,
h
[7] H. Zhu, X. Zhang, B. Zuo, Hebei Daxue Xuebao, Ziran Kexueban 16 (1996) 58.
[8] (a) C. Di Nicola, J. Ngoune, Effendy, C. Pettinari, B.W. Skelton, A.H. White, Inorg.
Chim. Acta 360 (2007) 2935;
range = 3.24–63.96°, Index ranges ꢀ8 6 h 6 14, ꢀ14 6 k 6 15,
16 6 l 6 14, total/unique reflections: 10960/6359, data/restraints/
parameters: 6359/0/451, int = 0.0329, = 0.0410, wR = 0.1041
I > 2 (I)], R = 0.0453, wR
ꢀ
(
8
b) A.H. Othman, H.-K. Fun, K. Sivakumar, Acta Crystallogr., Sect. C 52 (1996)
43;
R
R
1
2
[
9
r
1
2
= 0.1058 [all data], completeness to hmax
:
(c) M.C. Gimeno, P.G. Jones, A. Laguna, C. Sarroca, Polyhedron 17 (1998) 3681;
(d) V. Venkatachalam, K. Ramalingam, Synth. React. Inorg. Met. Org. Chem. 26
2
7.8%/63.96°, Goodness-of-fit S on F : 0.987, largest difference in
(
1996) 112.
9] (a) Ö. Güzel, A. Salman, Bioorg. Med. Chem. 14 (2006) 7804;
b) S. Ozkirimli, T.I. Apak, M. Kiraz, Y. Yegenoglu, Arch. Pharm. Res. 28 (2005)
213.
ꢀ
3
peak/hole: 1.127/ꢀ0.781 eÅ
.
[
(
1
4
.3.4.3. Crystal data for 12bꢃCH
2
Cl
2 2 2 2
. C44H46AgCl NOP S , M = 909.65
[
[
10] F. Bonati, R. Udo, J. Organomet. Chem. 10 (1967) 257.
11] R. Kellner, G.S. Nikolov, N. Trendafilova, Inorg. Chim Acta 84 (1984) 233.
ꢀ1
ꢀ
g mol , T = 100 K, k = 1.54184 Å, triclinic, P1, a = 12.5600(5) Å,
b = 13.0691(7) Å, c = 14.4305(8) Å,
a
q
= 96.482(5)°, b = 93.827(4)°,
calc = 1.450 g cm , F(000) =
[12] H. Friebolin, G. Schilling, L. Pohl, Org. Magn. Reson. 12 (1979) 569.
[13] S.M. Socol, R.A. Jacobson, J.G. Verkade, Inorg. Chem. 23 (1984) 88.
3
ꢀ3
c
= 116.739(5)°, V = 2083.39(18) Å ,
[
14] (a) U. Siegert, H. Hahn, H. Lang, Inorg. Chim. Acta 363 (2010) 944;
b) E.L. Muetterties, C.W. Alegranti, J. Am. Chem. Soc. 92 (1970) 4114;
(c) E.L. Muetterties, C.W. Alegranti, J. Am. Chem. Soc. 94 (1972) 6386;
d) Z. Yuan, N.H. Dryden, J.J. Vittal, R.J. Puddephatt, Chem. Mater. 7 (1995)
696;
e) R.G. Goel, P. Pilon, Inorg. Chem. 17 (1978) 2876.
9
36, crystal dimensions 0.22 ꢂ 0.14 ꢂ 0.03 mm, Z = 2, minimum/
(
ꢀ1
maximum transmission: 1.00000/0.43895,
l = 6.993 mm , h
(
1
(
range = 3.11°–65.48°, Index ranges ꢀ14 6 h 6 14, ꢀ13 6 k 6 15,
16 6 l 6 17, total/unique reflections: 11958/7019, data/restraints/
parameters: 7019/52/504, Rint = 0.0277, R = 0.0442, wR = 0.1139
I > 2 (I)], R = 0.0523, wR = 0.1166 [all data], completeness to hmax
7.8%/65.48°, Goodness-of-fit S on F : 0.966, largest difference in
ꢀ
1
2
[15] R. Mothes, Y. Shen, A. Jakob, B. Walfort, T. Rüffer, S.E. Schulz, R. Ecke, T.
Gessner, H. Lang, Dalton Trans. 39 (2010) 11235.
[16] M.D. Gordon, L.D. Quin, J. Magn. Reson. 22 (1976) 149.
[
r
1
2
:
2
9
[
17] S. Berger, S. Braun, H.-O. Kalinowski, (1992) in NMR-Spektroskopie von
Nichtmetallen, Vol. 2, G. Thieme Verlag, Stuttgart, Engl Ed., Wiley VCH Verlag
GmbH, Weinheim.
ꢀ
3
peak/hole: 1.403/ꢀ0.784 eÅ
.
[
[
18] A.H. Othman, H.-K. Fun, K. Sivakumar, Acta Crystallogr., Sect. C 52 (1996) 843.
19] (a) R. Nomura, M. Kori, H. Matsuda, Chem. Lett. (1985) 579;
Acknowledgments
(
b) R. Nomura, K. Kanaya, H. Matsuda, Ind. Eng. Chem. Res. 28 (6) (1989) 877.
We are grateful to the Deutsche Forschungsgemeinschaft (IRTG,
Materials and Concepts for Advanced Interconnects, GRK 1215) for
generous financial support. We acknowledge Prof. Michael
Mehring and Dr. Maik Schlesinger for XRPD measurements.
[20] R. Mothes, A. Jakob, T. Waechtler, S. E. Schulz, T. Geßner, H. Lang, Eur. J. Inorg.
Chem. submitted. http://dx.doi.org/10.1002/ejic.201403182
[
21] (a) A. Grodzicki, I. Łakomska, P. Piszczek, I. Szyma n´ ska, E. Szłyk, Coord. Chem.
Rev. 249 (2005) 2232;
(b) A. Jakob, Y. Shen, T. Wächtler, S.E. Schulz, T. Gessner, R. Riedel, C. Fasel, H.
Lang, Z. Anorg. Allg. Chem. 634 (12–13) (2008) 2226. and references cited
therein.
Appendix A. Supplementary material
[22] (a) E.W. Tyler III, M.B. Dines, US Patent no. 3776972, 1973. (b) E.W. Tyler III,
M.B. Dines, US Patent no. 3933878, 1976.
[
[
23] K. Okumura, S. Kouyama, J. Photopolym. Sci. Technol. 8 (3) (1995) 365.
24] (a) G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467;
(b) G.M. Sheldrick, SHELXL-97 Program for Crystal Structure Refinement,
Universität Göttingen, 1997.
CCDC 1032495 and 1032496 contain the supplementary crystal-
lographic data for 12a and 12b respectively. These data can be
obtained free of charge from The Cambridge Crystallographic Data