The Sterically Demanding Thiosilyl Group SSi(SiMe3)3as a Ligand in Transition Metal Chemistry

Article abstract of DOI:10.1002/zaac.201600137

The increasing number of metalloid clusters, synthesized in the last couple of years, gives new insights into the formation process of metals or semi-metals. Metalloid clusters of the transition metals, especially the coinage metals are thereby of particu

Full text of DOI:10.1002/zaac.201600137

Journal of Inorganic and General Chemistry
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Zeitschrift für anorganische und allgemeine Chemie
DOI: 10.1002/zaac.201600137
The Sterically Demanding Thiosilyl Group SSi(SiMe3)3 as a Ligand in
Transition Metal Chemistry
Matthias Kotsch,[a] Christian Gienger,[a] Claudio Schrenk,[a] and Andreas Schnepf*[a]
Keywords: Crystal structures; Gold; Coinage metals; Silyl ligands; Metalloid clusters
Abstract. The increasing number of metalloid clusters, synthesized in
the last couple of years, gives new insights into the formation process
of metals or semi-metals. Metalloid clusters of the transition metals,
especially the coinage metals are thereby of particular interest and the
number of structurally characterized metalloid gold clusters has in-
creased over the last decade. Most of these clusters are stabilized via
aryl thiolate ligands. Herein, the synthesis and crystal structures of the
lithium and potassium salts of the bulky SSi(SiMe3)3 ligand are pre-
sented together with the synthesis of suitable MI precursors (M = Cu,
Ag, Au) for further build-up reactions to metalloid clusters.
SePh with a low steric demand. As bulky ligands, like
Si(SiMe3)3 (Hyp) or N(SiMe3)2, are useful in the chemistry of
nanoscaled metalloid clusters of the elements of group 13 and
14,[9] it was wondered if it is possible to use such bulky ligands
also in the chemistry of metalloid clusters of coinage metals
and in the following a first step into this direction is presented.
Introduction
The chemistry of coinage metal nanoparticles has increased
in the last couple of years, whereby a prominent example is
the metalloid Au cluster Au55Cl6(PPh3)12,[1] which was synthe-
sized by Schmid et al. over 30 years ago via the reduction of
PPh3AuCl. However, the exact structure of this metalloid clus-
ter could not be determined, as it is not obtained as single
crystals up to now. The first example of a structurally well
Results and Discussion
characterized metalloid gold cluster Au102(SR)44 (R
=
S–C6H4–COOH) was presented by Kornberg et al. in 2007.[2]
The structural characterization thereby revealed that within the
multishell cluster unexpected and unusual arrangements of
gold atoms are realized; namely a pentagonal bipyramidal Au7
unit in the center.[3] After this breakthrough, a variety of fur-
ther examples of structurally well-characterized Au and Ag
clusters were presented, i.e. beside small compounds, like
[Au13Cl2(PPh2Me)10]2+,[4] also average sized clusters, like
[Ag44R30]4– (R = S–C6H4–COOH)[5] as well as other large
metalloid clusters, like Au130(p-MBT)50 (p-MBT = S–C6H4–
Me)[6] or Au133(TBBT)52 (TBBT = S–C6H4–tBu)[7] could be
synthesized, sometimes in quite high yields. Within the ma-
jority of these compounds chalcogenide-based ligands are used
to create bridging M–E–M moieties (M = Ag, Au, E = S, Se,
Te) in the outer sphere of the cluster, a structural motive also
found in metal chalcogenides, like Au2S.[8]
The Si(SiMe3)3 (Hyp) ligand was recently used by Klink-
hammer et al. for coinage metals, where they obtained a vari-
ety of gold silanide compounds, such as KAu(Hyp)2 or
K2Au4(Hyp)4 in the reaction of AuI with KHyp.[10] However,
the easiest way to introduce the Hyp ligand in coinage metal
chemistry might be as its thiolate, as it was reported by Arnold
et al. during the synthesis of LAuSHyp (L = Ph3P).[11] As this
is the only example of a coinage metal compound exhibiting
the SHyp ligand, whose composition is based on mass spectro-
metric and NMR spectroscopic investigations, it was tried to
build up a sustainable reaction pathway to sterically de-
manding group 11 metal thiolates. As already described in the
literature,[12] silanides like Hyp are easily oxidized by the
heavier chalcogenides by adding the pure elements to a solu-
tion of MHyp (M = Li, K) in thf.[13] Although this reaction is
long known, to date no crystal structure of the corresponding
lithium or potassium compound MSHyp was presented. There-
fore, to obtain a stable structural basis, it was first of all tried
to obtain single crystals of the MSHyp compounds suitable for
X-ray crystal structure analysis. In case of the lithium com-
pound, useful single crystals (colorless blocks) are obtained
from diethyl ether at –28 °C.
Most of the thiolates or selenolates used to date are classical
organic compounds like StBu, p-mercaptobenzoic acid, or
* Prof. Dr. A. Schnepf
Fax: +49-7071-28-2436
E-Mail: andreas.schnepf@uni-tuebingen.de
[a] Institut für Anorganische Chemie
Chemistry Department
[(thf)2LiSSi(SiMe3)3]2 (1Li) crystallizes in the triclinic space
University Tübingen
¯
group P1 with an inversion center inside the molecule (Fig-
Auf der Morgenstelle 18
72076 Tübingen, Germany
ure 1). In the asymmetric unit two similar half molecules are
found. The structure of 1Li can be described as a LiSHyp dimer
with two coordinating thf molecules per lithium cation. The
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201600137 or from the au-
thor.
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S–Si single bond (211 pm) is slightly shorter than the sum of
the covalent radii (219 pm),[14] whereas the averaged Si–Si
distances are with 235 pm in the range, well-known for Si–Si
single bonds in silanides.[15]
Figure 2. Molecular structure of [(18-crown-6)KS(Si(SiMe3)3] (1K) in
the solid state. All atoms are shown as their thermal ellipsoids with
50% probability. Selected bond lengths /pm and angles /°: K1–S1
311.09(12), K1–O116 289.3(2), S1–Si1 209.25(12), Si1–Si11
235.43(14), Si1–Si12 233.85(13), Si1–Si13 235.32(13); Si1–S1–K1
129.11(5), S1–Si1–Si11 111.82(5), S1–Si1–Si12 109.22(5), S1–Si1–
Si13 110.83(5), Si12–Si1–Si11 109.28(5), Si12–Si1–Si13 109.43(5),
Si13–Si1–Si11 106.20(5), C11–Si11–Si1 110.58(14).
Figure 1. Molecular structure of [(thf)2LiS(Si(SiMe3)3]2 (1Li) in the
solid state. All atoms are shown as their thermal ellipsoids with 50%
probability. All carbon, hydrogen, and oxygen atoms are shown with
70% transparency for clarity. Selected bond lengths /pm and angles
/°: S(2)–Si(2) 210.15(11), S(2)–Li(2) 242.4(5), S(2)–Li(2)’ 243.0(5),
Si(2)–Si(21) 234.17(11), O(201)–Li(2) 196.0(6), O(206)–Li(2)
193.9(5); Si(2)–S(2)–Li(2) 133.89(13), Si(2)–S(2)–Li(2)’ 131.99(12),
Li(2)–S(2)–Li(2)’ 92.92(16), S(2)–Si(2)–Si(23) 106.66(5), S(2)–Si(2)–
Si(22) 109.91(5), S(2)–Si(2)–Si(21) 108.90(5), Si(22)–Si(2)–Si(21)
109.85(5), S(2)–Li(2)–S(2)’ 87.07(16).
Trying to crystallize the heavier alkaline metal compound
KSHyp 1K in the same way from a diethyl ether solution only
leads to small colorless blocks, which cannot be mounted on
a diffractometer without decomposition, which might be due
to a high amount of co crystallized ether molecules. Therefore,
to obtain a better crystallizing isomer the cation complexing
agent 18-crown-6 was added to the solution, leading indeed to
more stable colorless block like single crystals of 1K, suitable
for X-ray crystal structure analysis (Figure 2).
¯
1K crystallizes also in the triclinic space group P1, but now
as a monomer, due to the saturation of the coordination sphere
of the potassium cation by the crown ether, i.e. only one potas-
sium–sulfur contact is formed in the solid state. The S–Si and
Si–Si bond lengths are similar to the lighter congener 1Li. The
compounds 1Li and 1K might be used as precursors for the
synthesis of coinage metal compounds of the general formula
MSHyp (M = Au, Ag, Cu), which may be useful starting com-
pounds for the synthesis of larger metalloid coinage metal clus-
ters via reduction with NaBH4.
Figure 3. Molecular structure of Ph3PAuSHyp (2) in the solid state.
All atoms are shown as their thermal ellipsoids with 50% probability.
Selected bond lengths /pm and angles /°: Au1–P1 225.88(10), Au1–
S1 229.23(10), P1–C1A 181.8(4), S1–Si1 214.81(15), Si1–Si13
234.49(16); P1–Au1–S1 172.57(4), C1A–P1–Au1 115.14(13), Si1–
S1–Au1 105.56(5), S1–Si1–Si13 112.89(7).
unit. The donor molecule PPh3 and the SHyp ligand are bound
In a first reaction, a salt metathesis reaction of LiSHyp 1Li to the gold atom almost linear (angle P1–Au1–S1: 172°) as it
and the commercially available gold(I) precursor Ph3PAuCl is often observed for gold(I) compounds, e.g. in the precursor
was performed, leading after work-up to colorless crystals of Ph3PAuCl.[16] The intermolecular Au–Au distance (590 pm) is
the expected compound Ph3PAuSHyp (2) (Figure 3).
far away from aurophilic interactions, therefore 2 is best de-
Another possible synthesis of 2 as already described in the scribed as a PPh3 stabilized AuSHyp monomer. Crystals of 2
literature[11] applies the reaction of the thiol HSHyp with are stable in air and can be stored over weeks. However, after
Ph3PAuN(SiMe3)2. However, a structural characterization of 2 dissolving in thf, decomposition takes place within a few
was missing up to now. Compound 2 crystallizes in the mono- hours, leading to a dark purple to black solution of unknown
clinic space group P21/c with one molecule in the asymmetric composition.
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Donor-stabilized gold(I) chloride is easily available by re- the gold atom. Beside this the tetramerization in case of copper
acting HAuCl4 with ethanol in the presence of triphenylphos- is independent of the type of donor. Nevertheless, also linear
phine. A similar way for synthesizing a precursor for the ligh- arrangements of CuI thiolates are known, e.g. the cuprate
ter congener silver fails due to the fact, that no silver(III) com- [Cu(SSi(ODipp)3)2]– (Dipp = 2,6-diisopropylphenyl), which
pound is available for reduction. Another problem is the low was synthesized from CuCl without any donor molecule.[25]
solubility of silver(I) halides in protic and aprotic solvents. As
a consequence, a salt metathesis reaction is impossible in case
of silver. However, silver(I) thiolates are well-known, e.g. the
tetrameric compound [AgSSi(OtBu)3]4, which was synthesized
by Wojnowski et al.[17] by the reaction of an aqueous solution
of AgNO3 with a benzene solution of HSSi(OtBu)3. Conse-
quently a similar two-phase reaction by adding a toluene solu-
tion of HSHyp to an aqueous solution of AgNO3 was chosen,
which yields after work-up procedures colorless needles of
(AgSHyp)4·Si2(SiMe3)6 (3·4), where the anticipated AgI com-
pound 3 co-crystallizes with the side product 4. The structural
arrangement is similar to the one found in the lighter congener
(CuSHyp)4.[18]
In case of copper, from a synthetic point of view the situa-
tion is similar to gold, as a variety of donor stabilized copper(I)
chlorides like (Ph3P)nCuCl (n = 1–3),[19,20] are known that are
soluble in organic solvents and which are prepared by the reac-
tion of CuCl with PPh3 in hot ethanol. Thus, a salt metathesis
reaction with the Li thiolate 1Li in toluene might be possible
and NMR spectroscopic monitoring shows a straightforward
reaction to yield one main product without detectable side
products. However, crystallization of this product failed due to
the large excess of free PPh3 in solution, which crystallizes
each time together with the product. Therefore it was tried to
avoid well-crystallizing donors, applying (tht)CuCl (5) (tht =
tetrahydrothiophene)[21] as the CuI precursor. The reaction of
Figure 4. Molecular structure of (CuSHyp)4 (6) without Me groups
for clarity (thermal ellipsoids with 50% probability). Selected bond
lengths /pm and angles /°: Cu1–Cu2 273.07(7), Cu1–S1 216.36(12),
Cu1–S4 215.71(12), Cu1–Cu4 316.46(8), Cu2–S1 216.23(12), Cu2–
S2 214.95(12), Cu2–Cu3 316.30(8), Cu3–Cu4 270.17(7), Cu3–S3
216.27(13), Cu3–S2 215.23(13), Cu4–S4 214.69(12), Cu4–S3
(tht)CuCl (5) with 1Li in toluene was monitored by NMR spec- 215.24(12), S2–Si2 218.92(16), Si2–Si22 234.35(19); S4–Cu1–S1
177.03(5), S2–Cu2–S1 173.11(5), Cu2–S1–Cu1 78.28(4), S2–Si2–
troscopy. The crude reaction product shows the same reso-
Si22 112.78(7), Cu1–Cu2–Cu3 89.67(2), Cu2–Cu3–Cu4 90.32(2).
nances within the SiMe3 region as observed during the reaction
of (Ph3P)nCuCl (n = 1–3) with 1Li. This implies that the kind
of donor does not have an influence on the resulting Hyp con-
taining compounds. However, now free tht is easily removed
from the reaction mixture by evaporating due to its low boiling
point (121 °C) and now after work-up procedures the reaction
product (CuSHyp)4 (6) was obtained in the form of colorless
needles.
Compound 6 (Figure 4) crystallizes in the monoclinic space
group C2/c. The metal atoms are arranged in the form of a
planar four-membered ring with Cu–Cu–Cu angles of
almost 90°. However, not a square planar arrangement is
formed, but a rectangular one, as two strongly different Cu–
Cu bond lengths of 273 pm and 316 pm are found. Similar
arrangements are observed e.g. in the isostructural compounds
(CuSSi(OtBu)3)4,[22] (CuSSiPh3)4,[23] and (CuSSiPhtBu2)4,[24]
where beside rectangular also ideal square planar arrangements
are observed, which may be due to packing effects. Comparing
6 with the monomeric gold compound Ph3PAuSHyp (2) indi-
cates that the donor molecule has a big influence on the molec-
ular structure. Similar tetrameric gold(I) species are also
known, e.g. [AuSC(SiMe3)3]4,[11] where (tht)AuCl was used as
To check if the thiolate ligand can also be used for other
transition metal ions as a proof of principle the reaction of
1Li with ZnCl2 was investigated, which leads after work-up to
colorless blocks of (thf)2LiZn(SHyp)3 (7) from a pentane ex-
tract (Figure 5).
Compound 7 crystallizes in the monoclinic space group
P21/c and can be described as an adduct of (thf)2LiSHyp and
Zn(SHyp)2. In 7 the zinc atom has the unusual coordination
number 3 with a planar arrangement of the sulfur atoms of the
surrounding ligands (sum of S–Zn–S angles: 360°). However,
the S–Zn–S angles deviate from an ideal trigonal arrangement,
which might be explained by the coordination of the lithium
cation to one of the three sulfur (S2) atoms. The lithium cation
is further saturated by two thf molecules, leading also to the
unusual low coordination number of three for the lithium cat-
ion. The coordination of the lithium cation to [Zn(SHyp)3]–
gives a neutral molecule, which is also good soluble in pent-
ane. Planar arrangements are unusual for three coordinated
zinc(II) compounds with monodentate ligands and to date only
another example, (Et4N)Zn(SAd)3 (Ad = adamantyl)[26] is
known. However, in case of (Et4N)Zn(SAd)3 the ammonium
a starting material. Consequently, in the case of 2, the donor cation shows no contact to the anion leading to a nearly sym-
PPh3 hinders oligomerization due to the strong interaction with metric planar arrangement around the zinc atom (S–Zn–S
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were dried with sodium and purified via distillation. All solids were
stored in a glovebox under argon atmosphere. NMR spectroscopic
measurements were done at a Bruker DRX-250. The chemical shifts
are given in ppm against external standards SiMe4 (1H, 13C, 29Si) and
85% phosphoric acid (31P), respectively. C6D6 was dried with 3 Å
molecular sieves. The INEPT pulse program was used in all shown
29Si NMR experiments. Elemental analysis failed for all compounds
due to incomplete combustion leading to strongly different values from
a pure crystalline sample.
Synthesis of (thf)2LiSSi(SiMe3)3 (1Li): Freshly prepared
[28]
(thf)3LiSi(SiMe3)3
(48.4 g, 100 mmol) was dissolved in thf
(200 mL). The mixture was cooled to –20 °C and sulfur (3.2 g,
100 mmol) was added whilst stirring. The mixture was allowed to
reach room temperature within 12 h. The solvent was removed in
vacuo leading to a gray solid, which was recrystallized from diethyl
ether to give (thf)2LiSSi(SiMe3)3 (1Li) as colorless crystals (yield
1
32.1 g; 75 mmol; 75%). H NMR (250 MHz, C6D6): δ = 0.41 (s, 27
H, SiMe3), 1.43 (m, 8 H, THF), 3.73 (m, 8 H, THF) ppm. 13C{1H}
NMR (62.9 MHz, C6D6): δ = 0.64 (s, SiMe3), 25.48 (s, THF), 68.49
(s, THF) ppm. 29Si NMR (49.7 MHz, C6D6): δ = –14.12 (decet,
SiMe3), –60.21 [m, Si(SiMe3)3] ppm.
Synthesis of (18-crown-6)KSSi(SiMe3)3 (1K): Freshly prepared
Figure 5. Molecular structure of (thf)2LiZn(SHyp)3 (7) without Me
[29]
KSi(SiMe3)3
(12.3 g, 31 mmol) was dissolved in thf (15 mL). The
groups for clarity (thermal ellipsoids with 50% probability). The thf
molecules are simplified as wires for clarity. Selected bond lengths
/pm and angles /°: Zn1–S1 222.94(7), Zn1–S2 230.94(7), Zn1–S3
223.44(8), S1–Si1 214.62(10), Si1–Si11 234.09(11), S2–Li14
241.3(4), Li14–O101 189.9(6); S1–Zn1–S2 126.62(3), S1–Zn1–S3
125.80(3), S3–Zn1–S2 107.57(3), Si1–S1–Zn1 115.69(4), Zn1–S2–
Li14 106.37(14), O101–Li14–S2 117.8(3).
mixture was cooled to 0 °C. Elemental sulfur (1 g, 31 mmol) was
added whilst stirring. The yellow mixture was stirred for 12 h reaching
room temperature. The solvent was removed in vacuo and the residue
was extracted with toluene. To this toluene extract, 18-crown-6 (8.2 g,
31 mmol) was added. Crystals of (18-crown-6)KSSi(SiMe3)3 (1K)
were obtained at –28 °C (yield 14.2 g; 23.8 mmol; 77%). 1H NMR
(250 MHz, C6D6): δ = 0.61 (s, 27 H, SiMe3), 3.22 (s, 24 H, 18-crown-
6) ppm. 13C{1H} NMR (62.9 MHz, C6D6): δ = 1.54 (s, SiMe3), 70.44
(s, 18-crown-6) ppm. 29Si NMR (49.7 MHz, C6D6): δ = –16.36 (decet,
SiMe3), –62.65 [m, Si(SiMe3)3] ppm.
angles vary in the range of 118.4° to 120.9°).[27] In other cases,
[24]
only heteroleptic compounds (ClZnSSitBu3)2
could be iso-
lated, where a dimerization leads to a Zn2S2 four-membered
ring.
Synthesis of Ph3PAuSSi(SiMe3)3 (2): 1Li (0.95 g, 2.2 mmol) dis-
solved in toluene (20 mL), was added at –10 °C to a solution of
Ph3PAuCl (1 g, 2 mmol) in toluene (10 mL). The mixture was stirred
for 1 h at –10 °C and 2 h at room temperature. All volatile components
were evaporated and the remaining solid was extracted several times
with pentane. Storing the pentane extract at –28 °C leads to crystals
of Ph3PAuSSi(SiMe3)3 (2) at –28 °C (yield 0.7 g, 0.94 mmol, 46%).
1H NMR (250 MHz, C6D6): δ = 0.46 (s, 27 H, SiMe3), 6.89–6.96 (m,
9 H, Ph3P), 7.34–7.44 (m, 6 H, Ph3P) ppm. 13C{1H} NMR (62.9 MHz,
C6D6): δ = 0.6 (s, SiMe3), 127.8 (d, Ph), 129.0 (d, Ph), 131.1. (s, Ph),
134.4 (d, Ph) ppm. 29Si NMR (49.7 MHz, [D8]THF): δ = –13.4 (decet,
SiMe3), –57.3 [m, Si(SiMe3)3] ppm. 31P{1H} NMR (25.8 MHz, C6D6):
δ = –37.93 (s, Ph3PAu) ppm.
Summary and Outlook
Thiolate ligands are useful compounds in coinage metal
chemistry and to date only few examples of bulky coinage
metal thiolates are known. However, the reaction of
LiSSi(SiMe3)3 1Li with group 11 halides leads to a variety of
monomeric and tetrameric MI species [MSHyp]n (M = Cu, Ag,
n = 4; M = Ph3PAu, n = 1), giving access to a variety of
coinage metal precursors with bulky thiolate ligands. In case
of Au and Cu the compounds are obtained in moderate yield
being thus a good base for further investigations, e.g. reduction
reactions to open the door to coinage metal clusters. The bulky
thiolate ligand SHyp can also be used for other transition met-
als as shown by the synthesis of the three-coordinate ZnII com-
pound (thf)2LiZn(SHyp)3 (7) exhibiting an unusual coordina-
tion sphere at the zinc atom. The synthesis and characterization
of the coinage metal compounds is thereby the first step for
the synthesis of metalloid clusters via reduction of the herein
presented MSHyp compounds (M = Au, Cu), which is part of
ongoing research.
Synthesis of [AgSSi(SiMe3)3]4·Si2(SiMe3)6 (3·4): AgNO3 (0.34 g,
2 mmol), dissolved in pure water (50 mL), was mixed with a solution
of HSSi(SiMe3)3 (0.56 g, 2 mmol) (synthesized according to the litera-
ture procedure[30]) in toluene (10 mL) under vigorous stirring. The
two-phase mixture was stirred for 30 min, in which a black precipitate
was formed. The mixture was filtered, the phases were separated and
the organic phase was washed three times with water. All organic
phases were combined and dried with Na2SO4. During a slow
evaporation process in an Erlenmeyer flask, few needles of
[AgSSi(SiMe3)3]4·Si2(SiMe3)6 (3·4) appeared (yield 0.04 g,
Experimental Section
1
0.02 mmol, 4%). H NMR (250 MHz, C6D6): δ = 0.41 (s, 108 H, 3
General Considerations: All experiments were done in an inert gas
SiMe3), 0.36 (s, 54 H, 4 SiMe3) ppm. 13C{1H} NMR (62.9 MHz,
atmosphere by using standard Schlenk techniques. All organic solvents C6D6): δ = 0.6 (s, 3 SiMe3), 4.5 (s, 4 SiMe3) ppm. 29Si NMR
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Table 1. Crystal data and details of structural determinations.
1Li
1K
2
6
7
Formula
Formula weight
T /K
C34H86Li2O4S2Si8
861.74
150
C21H51KO6SSi4
583.13
150
C27H42Si4PSAu
738.96
150
C36H108Si16S4Cu4
1373.06
150
C35H97LiO2S3Si12Zn
1055.69
150
Crystal system
Space group
a /Å
b /Å
c /Å
triclinic
P1
triclinic
P1
monoclinic
P21/c
9.5782(5)
11.2017(6)
31.6530(17)
90
97.7190(10)
90
3365.3(3)
4
4.638
1.458
39598
6887
0.0411
1.119
monoclinic
C2/c
51.236(3)
24.4910(17)
13.7908(10)
90
101.892(3)
90
16934(2)
8
1.336
1.077
54610
14895
0.0868
0.943
monoclinic
P21/c
20.8591(11)
28.2563(15)
23.8860(12)
90
114.5070(10)
90
12810.1(12)
8
0.731
1.095
90721
26108
0.0592
1.016
¯
¯
11.9780(8)
13.0772(10)
19.3472(14)
105.759(4)
98.788(4)
103.432(4)
2760.4(4)
2
0.299
1.037
55977
12655
9.8800(19)
11.562(2)
15.130(3)
94.589(3)
93.784(3)
100.611(3)
1687.6(6)
2
0.390
1.148
16115
6824
α /°
β /°
γ /°
V /Å3
Z
μ /mm–1
ρ /g·cm–3
Reflns. meas.
Independent reflns.
R(int.)
0.0768
1.013
0.0547
1.013
Goof
R1 (I Ͼ 2σ)
wR2 (all data)
0.0562
0.1490
0.0512
0.1285
0.0321
0.0598
0.0478
0.1109
0.0428
0.0984
(49.7 MHz, C6D6): δ = –9.6 (decet, 4 SiMe3), –12.6 (decet, 3 SiMe3),
–46.9 [m, 3 Si(SiMe3)3], –129.7 [m, 4 Si(SiMe3)3] ppm.
and refined by full-matrix least-square techniques (Programs used:
SHELXS and SHELXL).[31] The non-hydrogen atoms were refined
anisotropically and the hydrogen atoms were calculated using a riding
model. Partially occupied carbon atoms, which were used to describe
disorder within the structures, were refined isotropically. As in case of
6 solvent molecules are heavily disordered, which could not be reason-
ably modeled, SQUEEZE[32] was used to refine the structure. Table 1
contains the crystal data and details of the X-ray structure determi-
nation for all crystallized compounds.
Synthesis of [CuSSi(SiMe3)3]4 (6): (tht)CuCl (0.37 g, 2 mmol) was
dissolved in toluene (20 mL). 1Li, (0.86 g, 2 mmol) dissolved in tolu-
ene (20 mL), was added at room temperature and stirred for 30 min.
The mixture was filtered from any solid compounds and the solvent
was removed in vacuo. The residue was recrystallized from
benzene to yield air and moisture stable needle shaped crystals of
1
[CuSSi(SiMe3)3]4 (6) (0.41 g; 0.3 mmol; 60%). H NMR (250 MHz,
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-1472904 (1Li) CCDC-1472905 (1K), CCDC-1472910
(2), CCDC-1472906 (6), and CCDC-1472907 (7) (Fax: +44-1223-336-
033; E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
C6D6): δ = 0.43 (s, 27 H, SiMe3) ppm. 13C{1H} NMR (62.9 MHz,
C6D6): δ = 1.04 (s, SiMe3) ppm. 29Si NMR (49.7 MHz, C6D6): δ =
–11.9 (decet, SiMe3), –50.2 [m, Si(SiMe3)3] ppm.
Synthesis
of
(thf)2LiZn[SSi(SiMe3)3]3
(7)
and
(tmeda)2LiZn[SSi(SiMe3)3]3 (7Ј): 1Li (0.86 g, 2 mmol) and ZnCl2
(0.14 g, 1 mmol) were mixed in a round-bottom flask cooled to –40 °C.
The mixed solids were then dissolved in thf (30 mL). The reaction
mixture was stirred for 12 h, in which the solution was allowed to
reach room temperature. All volatile components were removed in
vacuo leading to a colorless powder, which was extracted with pentane.
Further concentration and storage overnight at –28 °C gives colorless
crystals of (thf)2LiZn[SSi(SiMe3)3]3 7 (yield 0.2 g, 0.2 mmol, 20%).
Supporting Information (see footnote on the first page of this article):
Crystal structure data and discussion of (AgSHyp)4•Si2(SiMe3)6 3•4
and [Li(TMEDA)2][Zn(SHyp)3] 7’are presented as well as the NMR
spectra (1H, 13C and 29Si) of 2, 3•4, 6, and 7.
1H NMR (250 MHz, C6D6): δ = 0.44 (s, 27 H, SiMe3) 1.34 (m, 8 H, References
thf), 3.58 (m, 8 H, thf) ppm. 13C{1H} NMR (62.9 MHz, C6D6): δ =
[1] G. Schmid, R. Pfeil, R. Boese, F. Bandermann, S. Meyer,
1.0 (s, SiMe3), 25.5 (s, thf), 68.6 (s, thf) ppm. 29Si NMR (49.7 MHz,
C6D6): δ = –11.92 (decet, SiMe3) –55.5 [m, Si(SiMe3)3] ppm.
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In a similar way, compound 7Ј was synthesized, adding dry TMEDA
(1 mL) to the colorless solution at –40 °C. Removing all volatile com-
pounds and extracting with toluene lead to a yellowish solution, from
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X-ray Crystallography: The data were collected at 150 K with a
Bruker APEXII microsource diffractometer employing monochro-
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Z. Anorg. Allg. Chem. 2016, 670–675
674
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
www.zaac.wiley-vch.de
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Received: April 19, 2016
Published Online: May 27, 2016
Z. Anorg. Allg. Chem. 2016, 670–675
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© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim