Synthesis and Crystal Structures of Copper Zinc Phenylthiolate and the First Copper Zinc Selenolate and Tellurolate Complexes

Article abstract of DOI:10.1002/zaac.201600426

Five copper zinc phenylchalcogenolate complexes [(iPr₃PCu)₃(ZnMe₂)₂(SPh)₃] (1), [(iPr₃PCu)₂(ZnPh)₄(SPh)₆] (2), [(iPr₃PCu)₂(ZnEt)₄(SPh)₆] (3), [(iPr₃PCu)₃(ZnEt)(SePh)₄] (4), and [(iPr₃PCu)₃Cu(iPr₃PZn)(TePh)₆] (5) were synthesized by the reaction of phosphine stabilized copper phenylchalcogenolate complexes with ZnR₂ (R = Me, Et, Ph) with and without additional chalcogenol. The novel mixed metal compounds were characterized by single-crystal X-ray structure analysis and NMR spectroscopy. 4 and 5 are the first examples of compounds with a Zn–Se–Cu or a Zn–Te–Cu linkage, respectively.

Full text of DOI:10.1002/zaac.201600426

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201600426
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Synthesis and Crystal Structures of Copper Zinc Phenylthiolate
and the First Copper Zinc Selenolate and Tellurolate Complexes
Daniel Fuhrmann,[a] Tobias Severin,[a] and Harald Krautscheid*[a]
Dedicated to Professor Evamarie Hey-Hawkins on the Occasion of her 60th Birthday
Abstract. Five copper zinc phenylchalcogenolate complexes ZnR2 (R = Me, Et, Ph) with and without additional chalcogenol. The
[(iPr3PCu)3(ZnMe2)2(SPh)3] (1), [(iPr3PCu)2(ZnPh)4(SPh)6] (2), novel mixed metal compounds were characterized by single-crystal
[(iPr3PCu)2(ZnEt)4(SPh)6] (3), [(iPr3PCu)3(ZnEt)(SePh)4] (4), and X-ray structure analysis and NMR spectroscopy. 4 and 5 are the first
[(iPr3PCu)3Cu(iPr3PZn)(TePh)6] (5) were synthesized by the reaction
of phosphine stabilized copper phenylchalcogenolate complexes with
examples of compounds with a Zn–Se–Cu or a Zn–Te–Cu linkage,
respectively.
Cu-Zn-Se and Cu-Zn-Te complexes have been published so
far. We recently reported on synthesis, structural characteriza-
tion, and thermolysis studies of a series of heteronuclear cop-
per zinc ethandithiolate complexes.[11] Herein we present the
synthesis and characterization of novel copper zinc phenyl-
chalcogenolate complexes including the first selenolate and
tellurolate complexes of this type.
Introduction
In the search for new and efficient materials as absorbers
for thin film solar cells Cu2ZnSnS4 (CZTS) becomes more and
more attractive. The direct bandgap of 1.45 eV and the high
absorption coefficient of 104 cm–1 are ideal for application in
thin film solar cell fabrication.[1] In addition, the bandgap can
be adjusted from 1.45 eV to 0.9 eV by substitution of sulfur
by selenium atoms. Several methods for formation of CZTS
thin films have been reported,[2–6] including spray pyrolysis
or aerosol assisted chemical vapor deposition.[3] A promising
approach might be the thermolysis of molecular precursor
complexes containing several of the required elements, Cu, Zn,
Sn and S or Se. Controlling the stoichiometric composition of
the deposited thin films is difficult and needs high experimen-
tal effort. Thus, the reduction to a three component system was
already realized using metal dithiocarbamates or xanthates as
precursors.[4,5] Further reduction to a two component system
using heteronuclear copper zinc complexes has been sug-
gested.[4]
In literature just a few examples for mixed copper-zinc com-
plexes with sulfur donor ligands are known. [CuZn(MDtc)4]
(MDTc = dimethyldithiocarbamate)[6] and complexes with di-
substituted thiourea ligands[7] contain copper atoms in oxid-
ation state +II. Using thiocarboxylate ligands two complexes
with Cu+ and Zn2+ ions could be synthesized.[8] G. Kociok-
Köhn et al. published the first complex with a CuI–(SR)–ZnII
linkage.[9] A Cu-Zn selenophenolate has been suggested
in a patent.[10] However, to the best of our knowledge no
Results and Discussion
Synthesis
The copper zinc complexes [(iPr3PCu)3(ZnMe2)2(SPh)3] (1),
[(iPr3PCu)2(ZnPh)4(SPh)6] (2), [(iPr3PCu)2(ZnEt)4(SPh)6] (3),
[(iPr3PCu)3(ZnEt)(SePh)4] (4), and [(iPr3PCu)3Cu(iPr3PZn)-
(TePh)6] (5) are synthesized starting from iPr3P stabilized
copper phenylthiolate, phenylselenolate, and phenyltellurolate
complexes,
[iPr3PCuSPh]3,
[(iPr3P)4(CuSePh)6],
and
[(iPr3P)3(CuTePh)4], respectively (Scheme 1).[12] Syntheses
were performed in two different ways: The reaction of
[iPr3PCuSPh]3 with ZnMe2 results in the Lewis acid base ad-
duct 1, whereas reaction with ZnPh2 gives 2 with monophenyl-
zinc groups. We assume the formation of phosphine stabilized
phenyl copper, which is known as highly soluble in organic
solvents.[13] Addition of ZnEt2 or Zn(iPr)2 to the copper com-
plex leads to crystallization of the starting material only. Crys-
tals of 1 are very sensitive towards air and dissolve at tempera-
tures above –50 °C. The reaction of [iPr3PCuSPh]3 with ZnEt2
and additional thiophenol results in the evolution of ethane and
crystallization of 3, which is isostructural to 2.
* Prof. Dr. H. Krautscheid
The reaction of the phosphine stabilized copper
selenophenolate [(iPr3P)4(CuSePh)6] or tellurophenolate
[(iPr3P)3(CuTePh)4] with ZnEt2 and additional equivalents of
chalcogenol yields complexes 4 and 5. While the formation
of 5 was also observed using Zn(iPr)2 and ZnPh2 as starting
compounds no products could be obtained by reaction of
[(iPr3P)4(CuSePh)6] with organozinc compounds other than
E-mail: krautscheid@rz.uni-leipzig.de
[a] Institut für Anorganische Chemie
Fakultät für Chemie und Mineralogie
Universität Leipzig
Johannisallee 29
04103 Leipzig, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201600426 or from the au-
thor.
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Scheme 1. Reactions starting from [iPr3PCuSPh]3, [(iPr3P)4(CuSePh)6] or [(iPr3P)3(CuTePh)4] with ZnR2 (R = Me, Et, Ph) with and without
additional chalcogenol.
[12]
ZnEt2. For formation of 4 and 5 additional iPr3P is necessary structure of the starting compound [iPr3PCuSPh]3
in com-
to saturate all the copper atoms with a phosphine ligand. In parison to the ZnMe2 adduct 1. Both complexes contain a six-
the synthesis of 4, ZnEt2 reacts with selenophenol, which is
generated in situ by the reaction of PhSeSiMe3 with ethanol.
In the synthesis of 5, ZnEt2 is first converted to zinc ethanolate
which reacts with PhTeSiMe3 with elimination of Me3SiOEt.
All ethyl groups originally bound to zinc are eliminated and a
iPr3P ligand coordinates to the zinc atom.
membered ring of alternating copper and sulfur atoms, the or-
ganic groups are oriented to the exterior. The six-membered
ring in [iPr3PCuSPh]3 is approximately planar, whereas in 1
the Cu3S3 ring adopts boat conformation. However, the struc-
tural change caused by coordination of two ZnMe2 molecules
to the sulfur atoms S2 and S3 is only small.
The long Zn–S bond lengths of 268.5(2) and 274.3(1) pm
and the C–Zn–C bond angles 145.9(2)° and 153.9(2)° confirm
the only weak interaction between zinc and sulfur atoms,
which is responsible for the low stability of 1 in solution as
well as in solid state; 1 loses ZnMe2 during drying in vacuo.
Compounds 2 and 3 crystallize in space groups P21/c and
Molecular Structures
Single crystals suitable for X-ray crystal structure analysis
of 1–5 were obtained at low temperatures. Crystallographic
data are reported in Table 1. Figure 1 illustrates the molecular Pbca, respectively. Nevertheless, the molecular structures of
both compounds are very similar (Figure 2). The cluster mol-
ecules of 2 and 3 are centrosymmetric and their cores can be
described as two connected six-membered rings in boat confor-
mation containing one copper, two zinc and three sulfur atoms
each. Both rings are related by inversion symmetry. A similar
structure motive was found in [(Ph3PCu)4(ZnCl)2(SEt)6],[9]
however, with two phosphine coordinated copper atoms in-
stead of ZnR groups. All zinc atoms in 2 and 3 are tetrahe-
drally coordinated by three sulfur atoms and one ethyl or
phenyl group, respectively. The thiophenolate ligands with S2
and S3 exhibit the same μ3 coordination mode and bind to Zn1
and Zn2 with bond lengths between 244.2(1) and 253.02(9) pm
as well as to Cu1 with bond lengths of 226.6(1) and
229.36(9) pm. S1 bridges two zinc atoms with shorter bond
lengths in the range of 236.22(9) to 238.77(9) pm.
Figure 1. Molecular structures of [iPr3PCuSPh]3 (left) and 1 (right).
Atoms are drawn as ellipsoids with 50% probability. Hydrogen atoms
and disorder of isopropyl groups are omitted for clarity.
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Table 1. Details of the X-ray crystal structure analyses of 1–5.
1
2
3
4
5
Formula
C49H90Cu3P3S3Zn2
1189.65
213(2)
C85H106Cu2P2S6Zn4 C62H92Cu2P2S6Zn4
C53H88Cu3P3Se4Zn C72H114Cu4P4Te6Zn
Molar mass M /g·mol–1
Temperature /K
Crystal color and shape
Crystal size /mm
Crystal system
Space group
a /pm
1770.55
1480.21
1389.97
213(2)
2188.64
213(2)
213(2)
240(2)
pink needle
0.20ϫ0.20ϫ0.80
monoclinic
P21/n
1467.24(8)
1563.21(7)
2556.15(16)
91.425(5)
5861.0(6)
4
colorless block
0.19ϫ0.20ϫ0.30
monoclinic
P21/c
pink block
0.44ϫ0.56ϫ0.62
orthorhombic
Pbca
colorless block
0.13ϫ0.17ϫ0.19
monoclinic
P21/n
yellow plate
0.08ϫ0.32ϫ0.41
trigonal
¯
R3
1386.55(6)
1900.80(9)
1855.16(8)
104.431(4)
4735.1(4)
2
1661.07(6)
1908.28(5)
2227.35(8)
1312.9(3)
2186.1(5)
2161.6(5)
91.79(2)
6201(2)
1446.48(7)
1446.48(7)
7568.2(6)
b /pm
c /pm
β /°
Cell volume / 106 pm3
Z
7060.2(4)
4
13713.4(18)
6
4
Calcd. density /g·cm–3
Absorption coefficient
μ /mm–1
1.348
2.096
1.242
1.641
1.393
2.186
1.489
1.590
3.853
3.154
θ range /°
Measured reflections
1.8–25.6
46378
1.7–25.0
28589
1.8–26.9
28013
1.7–25.0
34116
1.7–25.0
23094
Independent reflections (Rint
Observed reflections
[I Ͼ 2σ(I)]
)
10829 (0.0540)
6814
8203 (0.0451)
5124
7456 (0.0384)
5511
10908 (0.0843)
5496
5360 (0.0417)
3577
Parameters
553
479
342
596
234
R1 (observed reflections)
wR2 (all data)
0.0341
0.0783
0.8 and –0.4
0.0314
0.0781
0.6 and –0.2
0.0392
0.1161
0.8 and –0.4
0.0372
0.0681
0.5 and –0.3
0.0414
0.1121
0.9 and –0.7
Max. and min. residual e–
density /10–6 pm–3
The selenophenolate complex 4 crystallizes in space group
P21/n with one molecule in the asymmetric unit which con-
tains three trigonally coordinated copper atoms, one ZnEt unit,
and four selenophenolate ligands (Figure 3). The copper atoms
are arranged in the shape of a triangle and one iPr3P ligand is
binding to each copper atom. The phenylselenolate ligand with
Se1 bridges all three copper atoms with Cu–Se bond lengths
between 240.3(1) and 243.1(1) pm. Selenium atoms Se2, Se3,
and Se4 are doubly bridging and bind to one of the three cop-
per atoms [Cu–Se 236.9(1)–239.8(1) pm] and to Zn1 [Zn–Se
253.5(1)–255.3(1) pm]. The Zn–C distance with 199.3(7) pm
is similar to that in 3, in which bond lengths of 197.4(5) pm
and 199.8(7) pm are measured.
Figure 2. Molecular structures of 2 (top) and 3 (bottom). Atoms are
drawn as ellipsoids with 50% probability. Hydrogen atoms and disor-
der of the isopropyl groups in 2 are omitted for clarity. Symmetry code Figure 3. Molecular structure of 4. Atoms are drawn as ellipsoids with
(Ј) 1–x, 1–y, 1–z.
50% probability. Hydrogen atoms are omitted for clarity.
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The tellurophenolate complex 5 crystallizes in the trigonal but similar to the already mentioned example for a Zn–PR3
¯
space group R3 (z = 6) in an adamantane like structure, which distance of 241 pm. The presence of zinc atoms in the crystal
was also observed in the mixed copper gallium chalcogenolate structure is confirmed by thermolysis of 5 under inert atmo-
[(Et3P)3Cu4MeGa(TePh)6].[14] Basis is a six-membered ring in sphere, which results in a mixture of copper telluride and zinc
chair conformation with alternating copper (Cu1) and tellurium telluride as solid thermolysis products (Figure S23, Supporting
(Te2) atoms (Figure 4). Cu2 is located in the center of the ring Information).
and binds to Te2 and its symmetry equivalent atoms in a trigo-
nal planar fashion with a Cu2–Te2 distance of 261.48(8) pm.
Characterization of the Complexes by X-ray Powder
Diffraction and NMR Spectroscopy
The ring atoms together with three tellurium atoms Te1 and
¯
the apical zinc atom located on the 3 axis form an adamantane
framework. The coordination of a iPr3P ligand to Zn1
[Zn1–P1 247.0(4) pm] is unusual, however, Zn–PR3 bonds
have been reported, e.g., in [(MePPh2)Zn(SAr)2] (Ar = 2,4,6-
tert-butylbenzene)[15] with a Zn–P distance of 241 pm.
Complexes 2–5 crystallize phase pure as confirmed by
X-ray powder diffraction (PXRD, Figures S1–S5, Supporting
Information). The weakness of the Zn–S bond in 1 and the
high vapor pressure of ZnMe2 (boiling point 46 °C) lead to
elimination of ZnMe2. According to a Rietveld refinement of
the X-ray powder diffraction pattern of 1 after the drying pro-
cess the product consists of only 25 mol% of 1 besides
75 mol% of [iPr3PCuSPh]3. NMR spectroscopy confirms that
the coordinative Zn–S bond in 1 is also labile in solution. The
1H NMR spectrum of 1 in C6D6 represents exactly the spectra
of a mixture of ZnMe2 and [iPr3PCuSPh]3 (Figure S6, Sup-
porting Information). NMR spectra of 2–5 (Figures S7–S10,
Supporting Information) show broad signals due to exchange
reactions in solution even at low temperatures. In case of 5,
1
additional peaks in the 31P{1H} and H NMR spectra (Figure
S11, Supporting Information) indicate instability of 5 in solu-
1
tion. However, the H NMR intensity ratios of the different
signal groups in 2–5 confirm the molecular compositions
known from single crystal structure analyses.
Conclusions
Starting from phosphine stabilized copper phenylchalogen-
olate complexes and organozinc compounds ZnR2 (R = Me,
Et, Ph) five copper zinc phenylchalcogenolate complexes were
synthesized. All complexes could be isolated as single crystals
suitable for single crystal structure analysis. Whereas 1 is an
adduct complex of a copper thiophenolate complex and
ZnMe2, 3–5 were synthesized in presence of further equiva-
lents of chalcogenophenol leading to the cleavage of Zn–C
bonds. In complexes 4 and 5 copper and zinc atoms are
bridged by seleno- or tellurophenolate ligands, respectively. To
the best of our knowledge these are the first examples for mol-
ecules containing a Zn–E–Cu linkage (E = Se, Te).
Figure 4. Molecular structure of 5 (top) and cluster core of 5 (bottom).
Heavy atoms are drawn as ellipsoids with 50% probability, carbon
atoms in ball and stick representation. Hydrogen atoms and disorder
of the isopropyl groups are omitted for clarity. Symmetry codes (Ј)
–y, x–y, z; (ЈЈ) –x+y, –x, z.
In contrast to the other copper zinc chalcogenolate com-
plexes, in 5, the copper atoms Cu1 are tetrahedrally coordi-
nated by one phosphine ligand and three tellurium atoms. The
Cu1–Te distances are in the range of 261.48(4)–267.36(9) pm,
and the Cu–P distance to the disordered iPr3P ligands is
230(2) pm. Zn1 is also in a tetrahedral environment with
Zn–Te distances of 265.37(6) pm. Since X-ray structure analy-
sis cannot reliably distinguish between Cu+ and Zn2+ due to
the same number of electrons, the assignment as a zinc atom
is based on the distance between Zn1 and P1 of 247.0(3) pm
Experimental Section
General: All syntheses were performed applying Schlenk technique
in a nitrogen atmosphere or in a MBRAUN UniLab glove box. All
solvents were dried according to common methods and distilled prior
to use. ZnPh2 was sublimed after reaction of dried ZnCl2 with LiPh.[16]
ZnEt2 and ZnMe2 were distilled prior to use. iPr3P was obtained by
the reaction of iPrMgBr with PCl3.[17] PhSeSiMe3 was synthesized by
the reaction NaSePh, prepared by reduction of Ph2Se2 with Na in liquid
NH3, and Me3SiCl.[18] PhTeSiMe3 was synthesized from PhMgBr, Te,
and Me3SiCl.[19] The phosphine stabilized copper chalcogenolates
which is significantly longer than expected for a Cu–P bond were prepared according to reference[12]. All other starting materials
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are commercially available. NMR spectra were measured with a
PhSeSiMe3 (0.13 mL, 0.67 mmol), and ZnEt2 (0.07 mL, 0.67 mmol)
were added dropwise. During the addition of ZnEt2 the solution
warmed up and gas evolution started. After 3 h the volume of the
Bruker Avance DPX-400 spectrometer with 400 MHz 1H frequency.
Dried and distilled C6D6 was used as solvent for all complexes. 1H
NMR spectra were referenced to TMS as internal standard. 13C, 31P colorless solution was reduced to about 10 mL and stored for 5 d at
and 77Se NMR spectra were referenced using the Ξ-scale.[20] IR data 2 °C, which gave 500 mg (0.36 mmol, 54%) of 4 as colorless blocks.
were collected with a Bruker Tensor 27 FTIR spectrometer in ATR 1H NMR (400 MHz, C6D6, 25 °C, TMS): δ = 1.03 [dd, JHP = 13.5,
3
mode. Elemental analysis (C and H) were measured with a Vario El- 3JHH = 7 Hz, 56 H, P-(CH-(CH3)2)3 and Zn-CH2–CH3]; 1.61 (t, JHH
3
Heraeus, TG/DTA analysis was performed with a NETZSCH STA 449
= 7.5 Hz, 3 H, Zn-CH2–CH3); 1.66 [sep, 9 H, P-(CH-(CH3)2)3]; 7.00
F1 coupled to an Aëolus QMS 403 D mass spectrometer. The given (m, 12 H, p+m-H PhSe–); 8.05 (m, 8 H, o-H PhSe–). 31P{1H} NMR
decomposition temperatures represent the start of mass loss.
(162 MHz, C6D6, 25 °C, TMS): δ = 25 (br. s). 77Se{1H} NMR
(76 MHz, C6D6, 25 °C, TMS): δ = 50 (br. s). 13C{1H} NMR
(100 MHz, C6D6, 25 °C, TMS): δ = 5.8 (Zn–CH2–CH3); 13.6 (Zn–
CH2–CH3); 19.8 [2JCP = 4 Hz, P–(CH–(CH3)2)3]; 22.7 [1JCP = 14 Hz,
P–(CH–(CH3)2)3]; 124.6 (p-CH PhS–); 127.9 (CH PhS–); 134.5 (br.,
i-C PhS–); 135.2 (CH PhS–). C53H88Cu3P3Se4Zn: calcd. C 45.8, H
6.4%; found: C 45.1, H 6.5%. Decomposition temperature: 140 °C.
[(iPr3PCu)3(ZnMe2)2(SPh)3] (1): [iPr3PCuSPh]3 (500 mg, 0.5 mmol)
was dissolved in n-heptane (20 mL) and ZnMe2·2.5n-hexane (0.6 mL,
1.5 mmol) was added dropwise. After 3 h the colorless solution was
reduced to half the volume under reduced pressure. Storing the solution
for one week at –80 °C gave pink needles of 1. The crystals are very
sensitive towards air and dissolve at temperatures above –50 °C. Dry-
ing the crystals (yield 250 mg) in vacuo leads to loss of ZnMe2. Ac-
cording to Rietveld refinement of the PXRD data the composition of
the product after drying in vacuo was 29 wt% (25 mol-%) of 1 and 71
wt% (75 mol-%) of [iPr3PCuSPh]3. 1H NMR (400 MHz, C6D6, 25 °C,
[(iPr3PCu)3Cu(iPr3PZn)(TePh)6] (5): [(iPr3P)3(CuTePh)4] (777 mg,
0.5 mmol) was suspended in n-heptane (60 mL). Successively iPr3P
(0.1 mL, 0.5 mmol), ZnEt2 (0.2 mL, 2 mmol) and EtOH (0.12 mL,
2 mmol) were added dropwise. The suspension was cooled to 0 °C and
PhTeSiMe3 (0.37 mL, 2 mmol) was added dropwise. After 2 h at 0 °C
a yellow solid precipitated, which dissolved almost completely after
raising the temperature to 25 °C. Filtration gave a yellow solution,
which was stored at 2 °C for 5 d. A few yellow needles of
[(iPr3P)3(CuTePh)4] crystallized. The solution was separated by fil-
tration and stored at –25 °C for one week. 300 mg (0.14 mmol, 28%)
3
TMS): δ = –0.63 (br. s, 5 H, Zn-(CH3)2); 1.04 [dd, JHP = 13.5,
3
3JHH = 7 Hz, 54 H, P-(CH-(CH3)2)3]; 1.67 [sep, JHH = 7 Hz, 9 H,
P-(CH-(CH3)2)3]; 6.93 (m, 3 H, p-H PhS–); 7.07 (br. m, 6 H, m-H
PhS–); 7.93 (br. m, 6 H, o-H PhS–). 31P{1H} NMR (162 MHz, C6D6,
25 °C, TMS): δ = 24 (br. s). C46H81Cu3P3S3Zn0.5: calcd. C 52.7, H
7.8%; found: C 51.2, H 7.7%.
1
of 5 crystallized as yellow plates. H NMR (400 MHz, C6D6, 25 °C,
[iPr3PCu)2(ZnPh)4(SPh)6] (2): [iPr3PCuSPh]3 (500 mg, 0.5 mmol)
was dissolved in n-heptane (25 mL). A solution of ZnPh2 (330 mg,
1.5 mmol) in 25 mL n-heptane was added. After 2 h the yellow solu-
tion became turbid and was filtered. Storing the filtrate at 2 °C for one
week yields 250 mg (0.14 mmol, 56%) of 2·n-heptane crystallized as
colorless blocks. 1H NMR (400 MHz, C6D6, 25 °C, TMS): δ = 0.77
TMS): δ = 0.60–1.30 [br. m, 72 H, P–(CH–(CH3)2)3]; 1.70–2.10 [br.
m, 12 H, P–(CH–(CH3)2)3]; 6.50–7.10 (br. m, 18 H, p+m-H PhTe–);
7.70–8.20 (br. m, 12 H, o-H PhTe–). C72H114Cu4P4Te6Zn: calcd. C
39.5, H 5.3%; found: C 40.5, H 5.8%. Decomposition temperature:
80 °C.
3
3
[br. dd, JHP = 13.5, JHH = 7 Hz, 31 H, P–(CH–(CH3)2)3]; 0.83 [br.
X-ray Crystal Structure Analysis: Crystallographic data are given in
Table 1. Measurements were performed with a STOE IPDS or a STOE
IPDS 2T image plate diffractometer systems equipped with a sealed
Mo X-ray tube and a graphite monochromator crystal [λ(Mo-Kα) =
71.073 pm]. Data reduction and numerical absorption correction were
performed with STOE X-AREA[21] software. All structures were
solved with direct methods using SHELXS-2014 and refined with
SHELXL-2014.[22] With exception of disordered iPr groups, the non-
hydrogen atoms of the complexes were refined with anisotropic ther-
mal parameters. The coordinates of the hydrogen atoms were calcu-
lated for idealized positions. Diamond 3.2k was used for visualization
of the crystal structures.[23]
3
3
dd, JHP = 13.5, JHH = 7 Hz, 5 H, P–(CH–(CH3)2)3]; 1.09 [br. m, 5.2
H, P–(CH–(CH3)2)3]; 1.45 [br. m, 0.8 H, P–(CH–(CH3)2)3]; 6.79 (br.
m, 18 H, p+m-H PhS–); 7.19 (m, 12 H, p+m-H ZnPh); 7.69 (br. m, 8
H, o-H ZnPh); 7.83 (br. m, 12 H, o-H PhS–). 31P{1H} NMR (162 MHz,
C6D6, 25 °C, TMS): δ = 29 (br. s). C85H106Cu2P2S6Zn4: calcd. C 57.7,
H 6.0%; found: C 57.3, H 5.9%. Loss of heptane starts at 80 °C,
decomposition at 200 °C.
[(iPr3PCu)2(ZnEt)4(SPh)6] (3): [iPr3PCuSPh]3 (462.8 mg, 0.5 mmol)
was dissolved in n-heptane (20 mL). Successively PhSH (0.15 mL,
1.5 mmol) and ZnEt2 (0.15 mL, 1.5 mmol) were added dropwise. After
6 h colorless solid precipitated, which was dissolved by warming the
suspension at 50 °C for a few min.. The solution was filtered to remove
traces of copper and stored at 2 °C for 3 d. 530 mg (0.36 mmol, 95%)
of 3 crystallized as pink blocks. 1H NMR (400 MHz, C6D6, 25 °C,
TMS): δ = 0.88 [m, 44 H, Zn-CH2–CH3 and P-(CH-(CH3)2)3]; 1.43
[m, 18 H, Zn-CH2–CH3 and P-(CH-(CH3)2)3]; 6.92 (m, 6 H, p-H
PhS–); 7.03 (m, 12 H, m-H PhS–); 7.88 (m, 12 H, o-H PhS–). 31P{1H}
NMR (162 MHz, C6D6, 25 °C, TMS): δ = 28 (br. s). 13C{1H} NMR
(100 MHz, C6D6, 25 °C, TMS): δ = 4.6 (Zn–CH2–CH3); 13.3 (Zn–
Crystallographic data for the structures in this paper have been de-
posited 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-1514201, CCDC-1514202, CCDC-1514203, CCDC-
1514204, and CCDC-1514205 (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
CH2–CH3); 20.1 [2JCP = 3.7 Hz, P–(CH–(CH3)2)3]; 22.9 [1JCP
=
16 Hz, P–(CH–(CH3)2)3]; 125.5 (p-CH PhS–); 128.6 (CH PhS–); 133.1
(CH PhS–), 138.2 (br., i-C PhS–). C62H92Cu2P2S6Zn4: calcd. C 50.3,
H 6.3%; found: C 49.7, H 6.2%. Decomposition temperature: 140 °C.
The PXRD measurements were carried out with a STOE STADI-P
diffractometer (Debye-Scherrer setup) equipped with a sealed Cu
X-ray tube and
a
germanium(111) monochromator crystal
[λ(Cu-Kα1) = 154.060 pm]. Samples of the air sensitive complexes
were prepared in a glove box in a nitrogen atmosphere and filled in
glass capillaries (Hilgenberg, outer diameter 0.5 mm). Rietveld
[(iPr3PCu)3(ZnEt)(SePh)4]
(676 mg, 0.33 mmol) was dissolved in n-heptane (30 mL) to form a
(4):
[(iPr3P)4(CuSePh)6]·n-pentane
yellow solution. After addition of iPr3P (0.13 mL, 0.67 mmol) the analyses were performed with TOPAS 5 software using the fundamen-
solution became colorless. Successively EtOH (0.024 mL, 0.67 mmol), tal parameter approach.[24]
Z. Anorg. Allg. Chem. 0000, 0–0
www.zaac.wiley-vch.de
5
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
[6] A. V. Ivanov, T. Rodyna, O. N. Antzutkin, Polyhedron 1998, 17,
Supporting Information (see footnote on the first page of this article):
3101–3109.
X-ray powder diffraction patterns, NMR spectra, IR spectra, thermo-
gravimetric data and X-ray powder diffraction patterns of the
thermolysis products.
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[8] S. Singh, J. Chaturvedi, A. S. Aditya, N. R. Rajasekhar, S. Bhatta-
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[9] G. Kociok-Köhn, K. C. Molloy, A. L. Sudlow, Main Group Met.
Chem. 2015, 38, 117–119.
[10] H. Ogawa, Jpn. Kokai Tokkyo Koho, Patent 2013, JP 2013026541
A 20130204.
Acknowledgements
We thank Regina Zäbe for measuring NMR spectra. We gratefully
acknowledge financial support by European Science Foundation and
Universität Leipzig. This work was funded by the European Union and
the Free State of Saxony.
[11] D. Fuhrmann, S. Dietrich, H. Krautscheid, Chem. Eur. J. 2016, in
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[12] O. Kluge, K. Grummt, R. Biedermann, H. Krautscheid, Inorg.
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Keywords: Copper zinc phenylchalcogenolates; Crystal
structures; Coordination chemistry; Copper; Zinc
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Received: November 11, 2016
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www.zaac.wiley-vch.de
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
D. Fuhrmann, T. Severin, H. Krautscheid* ..................... 1–7
Synthesis and Crystal Structures of Copper Zinc Phenylthiolate
and the First Copper Zinc Selenolate and Tellurolate Com-
plexes
Z. Anorg. Allg. Chem. 0000, 0–0
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim