Formation of extended 1D and 2D coordination polymers in tetrathioether complexes of mercury(II) and copper(I): crystal structures of {{Ge(CH 2SPh)4HgBr2J and [{{Ge(CH2SPh) 4}Cu2l2</su

Article abstract of DOI:10.1002/zaac.200900003

A one-dimensional (ID) coordination polymer of stoichiometry [((Ge(CH ₂SPh)₄)HgBr₂}_n] (2b) has been prepared by treatment of HgBr₂ with the functionalized germane Ge(CH₂SPh)₄ (1b

Full text of DOI:10.1002/zaac.200900003

ARTICLE
DOI: 10.1002/zaac.200900003
Formation of Extended 1D and 2D Coordination Polymers in Tetrathioether
Complexes of Mercury(II) and Copper(I): Crystal Structures of
[{{Ge(CH2SPh)4}HgBr2}n] and [{{Ge(CH2SPh)4}(Cu2l2}}n]
Harmel N. Peindy,[a] Fabrice Guyon,[a] Abderrahim Khatyr,[a] Michael Knorr,*[a]
Viktoria H. Gessner,[b] and Carsten Strohmann*[b]
Dedicated to Professor Michael Veith on the Occasion of His 65th Birthday
Keywords: Mercury; Copper; Thioether complexes; Coordination polymers; Germanium
Abstract. A one-dimensional (1D) coordination polymer of stoichi-
ometry [{{Ge(CH2SPh)4}HgBr2}n] (2b) has been prepared by treat-
novel metal-organic polymer [{{Ge(CH2SPh)4}(Cu2I2)}n] (3),
which incorporates rhombic dinuclear Cu(µ-I)2Cu units within its
ment of HgBr2 with the functionalized germane Ge(CH2SPh)4 (1b), 2D sheet-like network, was obtained. The luminescence properties
which is acting as a tetradentate thioether ligands. The extended of 1b and 3 have been investigated both in solution and in the solid
structure results from weak intermolecular HgϪS interactions link-
ing the monomeric {Ge(CH2SPh)4}HgBr2 units, as established
state. Upon treatment of 1b with [{Re(µ-Br)(CO)3(THF)}2] the
mononuclear compound fac-[ReBr(CO)3{Ge(CH2SPh)4}] (4) is
using single-crystal X-ray diffraction. The effective coordination formed. In this chelate complex, two CH2SPh arms are ligated on
around the mercury atoms is best described as distorted octahedral.
ReI, the remaining two CH2SPh arms are dangling.
Upon reaction of CuI with 1b in a 2:1 metal-to-ligand ratio, the
work that tetrathioether ligands of type Si(CH2SR)4
(R ϭ Me, Ph) may be used as assembling ligands to con-
struct mono-dimensional coordination polymers of type
[{{Si(CH2SR)4}HgBr2}n] upon reaction with HgBr2 [15a,
b]. The heavier tin congener Sn(CH2SPh)4 (1c) has been
described 35 years ago [16], and the derivative
Sn(CH2SMe)4 has quite recently been employed as precur-
sor for the preparation of the 1D coordination polymer
[{{Sn(CH2SMe)4}(ZnCl2)2}n] [17].
Continuing our studies on multidentate thioethers, we
now set out to evaluate and compare the coordinative
properties of the tetrathioether ligand Ge(CH2SPh)4 (1b)
with those of its silicon analogue Si(CH2SPh)4 (1a) [7, 15c].
The synthesis and molecular structure of 1c has recently
been described by Strohmann et al. [18]. We report herein
on the preparation and crystallographic characterization of
metal-organic 1D and 2D networks of HgII and CuI in-
corporating this germanium-based ligand system and pre-
sent their luminescence properties. For comparison, a
mononuclear compound fac-[ReBr(CO)3{Ge(CH2SPh)4}]
has been prepared.
Introduction
Bi- and polydentate thioethers represent an emerging
class of flexible ligands for various applications such as mo-
lecular electronics, catalysis, stabilization of colloids, prep-
aration of self-assembled monolayers on gold surfaces, and
the elaboration of luminescent compounds [1Ϫ4]. Further-
more, they are particularly interesting since they can act as
flexible building blocks (tectons) with the ability to generate
diverse metal organic coordination networks in auto-
assembly processes [5]. In the past, Siemeling [3b],
Rabinovich [11Ϫ14] and our group [6Ϫ10] have reported on
the synthesis of silicon-based bidentate and tridentate
thioethers R4ϪnSi(CH2SR)n (n ϭ 2, 3; R ϭ Me, Ph) and
characterized a wide variety of transition metal complexes
in which they act as either terminal or bridging ligands.
More recently, we have demonstrated in a collaborative
* Prof. Dr. M. Knorr
E-Mail: michael.knorr@univ-fcomte.fr
* Prof. Dr. C. Strohmann
E-Mail: carsten.strohmann@uni-dortmund.de
[a] Institut UTINAM UMR CNRS 6213
´
´
Universite de Franche-Comte
Experimental Section
16, Route de Gray
25030 Besanc¸on, France
[b] Technische Universität Dortmund
Anorganische Chemie
MeCN was dried with molecular sieves before use, toluene with
sodium and dichloromethane with P4O10. IR spectra have been re-
corded with a Nicolet Nexus 470 spectrometer, UV/Vis spectra with
a Uvikon-XL spectrometer. The liquid and solid-state emission
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H. N. Peindy, F. Guyon, A. Khatyr, M. Knorr, V. H. Gessner, C. Strohmann
ARTICLE
spectra were recorded with a Jobin-Yvon Fluorolog-3 spectrometer
using a cylindrical 0.5 cm diameter quartz capillary with a scan
speed of 1 nm·sϪ1. Emission intensity are normalized for compari-
son. Elemental C, H analyses were performed with a Leco Elemen-
Crystallographic data for the structures (2b: CCDC-698030, 3:
CCDC-698029) has been deposited with the Cambridge Crystallo-
graphic Data Centre. Copies of the data can be obtained free of
charge on application to The Director, CCDC, 12 Union Road,
tal Analyser CHN 900. The 1H-NMR spectra were recorded at Cambridge CB2, 1EZ, UK (Fax: int.codeϩ44-1223-336-033;
300.13 MHz with a Bruker Avance 300 instrument. [{Re(µ-Br)
(CO)3(THF)}2] was prepared according to ref [19].
E-Mail for inquiry: fileserv@ccdc.cam.ac.uk; E-Mail for depo-
sition: deposit@ccdc.cam.ac.uk).
Preparation of 1D Polymer [{{Ge(CH2SPh)4}HgBr2}n] (2b)
Results and Discussion
To a suspension of HgBr2 (360.5 mg, 1 mmol) in toluene (10 mL)
was added 1b (565 mg, 1 mmol). The solution was heated to reflux
for 5 min and the stirred at 25 °C for 24 h. Layering the clear
solution with hexane afforded colorless crystals, suitable for X-ray
diffraction. Yield: 0.796 g, 81 %. Anal. C28H28Br2GeHgS4(925.82):
C, 36.32; H 3.05; found: C, 36.81; H 3.5 %. 1H NMR (CDCl3): δ ϭ
2.86 (s, 8 H, SiCH2), 7.15Ϫ7.42 (m, 20 H, C6H5).
Synthesis and Structural Characterization of 1D
Metallopolymer [{{Ge(CH2SPh)4}HgBr2}n] (2b)
The polymeric complex [{{Ge(CH2SPh)4}HgBr2}n] (2b)
was prepared by treatment of mercury(II) bromide with an
equimolar amount of ligand 1b (Scheme 1) in hot toluene
and isolated as white, air-stable solid in 58 % yield. It is
moderately soluble in chlorinated hydrocarbons and was
characterized by a combination of analytical and spectro-
scopic techniques. The 1H-NMR spectrum in CDCl3 exhib-
its a singlet resonance for the methylene protons at δ ϭ
2.86, which is slightly downfield-shifted relative to the free
ligand (δ ϭ 2.60) in the same solvent. The presence of only
one broadened signal for the four methylene groups even at
temperatures down to 243 K indicates a highly flexible (i.e.,
labile) system in solution. It is noteworthy that according
to studies by Goodall, no mercury-thioether adduct could
be obtained by treatment of HgBr2 with the tetrathioether
ligand C(CH2SPh)4 [21].
Preparation of 2D Polymer [{{Ge(CH2SPh)4}(Cu2I2)}n] (3)
To a suspension of CuI (382 mg, 2.0 mmol) in MeCN (10 mL) was
added 1b (565 mg, 1.0 mmol). The mixture was refluxed for 5 min,
then the solution was allowed to reach room temperature. After
one day, colourless crystals of 3b were formed. Yield 0.681 g, 72 %.
C28H28Cu2GeI2S4 (946.21): calcd. C 35.54, H 2.99; found C 35.89,
H 2.55.
Preparation of [ReBr(CO)3]2{(PhSCH2)4Ge)} (4)
[{Re(µ-Br)(CO)3(THF)}2] (211 mg, 0.25 mmol) was dissolved in
7 mL of dichloromethane and 1b (286 mg, 0.51 mmol) was added
to the solution. The reaction mixture was stirred at room tempera-
ture for 1h, then reduced to ca. 5 mL and layered with heptane.
Yield 0.347 g, 76 %. Anal. C31H28BrGeO3ReS4 (915.56): C, 40.67;
H, 3.08; S 14.01; found: C, 40.41; H, 3.23; S, 13.96. Ϫ IR(CH2Cl2):
ν(CO) ϭ 2039s, 1953s, 1913s cmϪ1
2.74 (d, HA, 2H, JHAHB ϭ 10.1 Hz), 3.79 (d, HB, 2H, JHAHB
.
1H NMR: δ ϭ 2.70 (s, 4H),
2
2
ϭ
10.1 Hz).
X-ray Structure Determinations
Suitable crystals of 2b and 3 were covered with inert oil (perfluoro-
poly-alkylether) and used for X-ray crystal structure determi-
nations. X-ray diffraction data of all structures were recorded at
193(2) K (compound 2b) and 173(2) K (compound 3) with the
Stoe-IPDS diffractometer. Graphite monochromated Mo-Kα radi-
˚
ation (λ ϭ 0.71073 A) was used. The crystal structure was solved
with direct methods and refined against F2 with the full-matrix
least-squares method (SHELXS-90, SHELXL-97) [20]. An numeri-
cal absorption correction was employed using the FACEIT-pro-
gram in IPDS (Stoe & Cie, 1999). For each structure, the non-
hydrogen atoms were refined anisotropically. All of the hydrogen
atoms were placed in geometrically calculated positions and each
was assigned a fixed isotropic displacement parameter based on a
riding-model. Refinement of the structures was carried out by full-
Scheme 1. E(CH2SPh)4 as building block for the assembly of 1D
and 2D polymers.
The molecular structure of 2b, which crystallizes in the
2
matrix least-squares methods based on Fo using SHELXL-97.
¯
triclinic crystal system, space group P1, was determined by
Information concerning the data collection and processing,
crystallographic parameters, and details on structure solution and
refinement are given in Table 3. Selected bond lengths and angles
are shown in Table 1 and Table 2, respectively.
single-crystal X-ray diffraction analysis. The polymeric
crystal structure is comparable to the silicon analogue,
[{Si(CH2SPh)4}HgBr2]n (2a) [15a, 22]. The repeating mo-
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Crystal Structures of [{{Ge(CH2SPh)4}HgBr2}n] and [{{Ge(CH2SPh)4}(Cu2l2}}n]
lecular motif, which is depicted in Figure 1, consists of a length to a HgBr2 moiety is evident. Even in the case of
fairly linear HgBr2 unit, which is coordinated by the sulfur an identical ϪCH2ϪSϪPh functionality, the HgϪS bond
atoms of the two PhSCH2-arms of ligand 1b. The resulting lengths are quite variable. For instance, in the 2D-coordi-
HgϪSϪCϪGeϪCϪS six-membered ring adopts a rather nation polymer [{{PhS(CH2)4SPh)4}Hg2Br4}n], the HgϪS
˚
twisted conformation.
bond lengths amount to 2.499(3) A [25], whereas in the 3D
coordination polymer [{{PhS(CH2)2SPh)4}Hg2Br4}n] sig-
˚
nificantly longer bond length of 2.8963(17) A have been ob-
served [26, 27].
In the crystal, [{{Ge(CH2SPh)4}HgBr2}n] (2b) forms an
extended polymeric structure due to two additional weak
intermolecular thioether interactions of 3.230(3) and
˚
3.237(3) A. This arrangement results in a distorted octa-
hedral environment of the mercury atoms with a total of
four HgϪS and two HgϪBr bonds. The corresponding cis-
angles in 2b span the range of 78Ϫ98°. Corresponding with
this pseudo-octahedral arrangement, the deviation from lin-
earity of the BrϪHgϪBr angle [169.882(17)°] is not very
pronounced. The HgϪBr bond lengths observed in 2b
˚
[2.4521(7) and 2.4540(6) A] correspond to those in 2a
˚
[2.4564(10) and 2.4571(10) A]. Similar values were also en-
countered in [{{PhS(CH2)4SPh)4}Hg2Br4}n] with 2.4404(8)
and 2.4592(7) A [25]. Interestingly, in the resulting infinite
Figure 1. Thermal ellipsoid plot of the molecular motif of
[{{Ge(CH2SPh)4}HgBr2}n] (2b).
˚
1D ribbon of [{{Ge(CH2SPh)4}HgBr2}n] (2b), all phenyl
substituents adopt an almost parallel syn-orientation with
a cutting angle of the normals of the two best planes of
2.31(1) and 1.65(1)° (Figure 2, Table 1). However, the short-
The HgϪS distances in the central motif of 2.988(3) and
˚
3.005(25) A are quite long, but similar to those [2.989(2)
˚
and 2.994(2) A] found in the silicon derivative 2a [15a].
˚
est distances between the planes amount to ϳ 3.66 A, thus
Significantly shorter bond lengths than those of 2a, b
have been reported for the dinuclear compound
[(1,4,7,10,13,16,19,22-octathiahiacyclotetracosane)(HgBr2)2].
In this thiacrown-ether complex, the mercury atom is lig-
ated through two short HgϪS bonds [2.581(4) and
˚
Table 1. Selected bond length /A and angles /° of compound 2b.
HgϪS(1)
HgϪS(2)
HgϪS(3)
HgϪS(4)
HgϪBr(1)
HgϪBr(2)
2.988(3)
3.005(2)
3.237(3)
3.230(3)
2.456(1)
2.457(1)
Br(1)ϪHgϪS(4)
Br(2)ϪHgϪS(1)
Br(2)ϪHgϪS(2)
Br(2)ϪHgϪS(3)
Br(2)ϪHgϪS(4)
S(1)ϪHgϪS(2)
S(1)ϪHgϪS(3)
S(1)ϪHgϪS(4)
S(2)ϪHgϪS(3)Ј
S(2)ϪHgϪS(4)
S(3)ЈϪHgϪS(4)Ј
94.54(4)
92.13(6)
95.52(5)
93.99(4)
77.93(4)
84.46(6)
98.18(4),
169.96(5)
170.03(3)
97.81(4),
81.26(5)
˚
2.835(4) A], whereas an additional third weak intermolecu-
˚
lar HgϪS bond of 3.110(4) A results in a distorted trigonal
bipyramidal arrangement to the metal atoms [23]. In the
macrocyclic dinuclear complex [(1,4,7,10,13,16-hexathiacy-
clooctadecane)(HgBr2)2] the average bond length between
Br(1)ϪHgϪBr(2)
169.88(2)
95.15(6)
92.17(5)
78.05(4)
the thia donors and the two HgII atoms amounts to Br(1)ϪHgϪS(1)
˚
Br(1)ϪHgϪS(2)
Br(1)ϪHgϪS(3)
2.772(5) A [24]. Consequently, no correlation between the
nature of a given thioether ligand and the HgϪS bond
Figure 2. View of the crystal structure of [{{Ge(CH2SPh)4}HgBr2}n] (2b) along the a-axis.
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H. N. Peindy, F. Guyon, A. Khatyr, M. Knorr, V. H. Gessner, C. Strohmann
ARTICLE
˚
excluding relevant πϪπ-stacking interactions. Conse- Table 2. Selected bond length /A and angles /° of 3. Symmetry
transformations used to generate equivalent atoms: #1 Ϫx ϩ 3/2,
y ϩ 1/2, Ϫz ϩ 1/2; #2 xϪ1/2, Ϫy ϩ 3/2, zϪ1/2; #3 x ϩ 1/2, Ϫy ϩ
3/2, z ϩ 1/2; #4 Ϫx ϩ 3/2, yϪ1/2, Ϫz ϩ 1/2.
quently, the syn-orientation can be attributed to packing
effects.
Synthesis and Structural Characterization of 2D Polymer
[{{Ge(CH2SPh)4}(Cu2I2)}n] (3)
Cu(1)ϪS(1)
Cu(1)ϪS(2)
Cu(2)ϪS(3)
Cu(2)ϪS(4)
Cu(1)ϪI(1)
Cu(1)ϪI(2)
Cu(2)ϪI(1)
2.358(1)
2.338(1)
2.361(1)
2.373(1)
2.6580(7)
2.5775(6)
2.6471(6)
Cu(2)ϪI(2)
Cu(1)ϪCu(2)
2.6210(7)
2.9433(9)
Auto-assembling processes between copper halides and
thioether ligands display fascinating networks incorporat-
ing various copper halide clusters as core motifs. The grow-
ing interest in the preparation of such CuX-containing
metal-organic frameworks is also due to promising photo-
physical properties of these materials, particularly
those possessing tetranuclear cubane-like Cu4X4L4
clusters [28Ϫ32]. The reaction of CuI with 0.5 equivalent
of 1b in acetonitrile gave colorless crystals of
[{{Ge(CH2SPh)4}(CuI)2}n] (3). Compound 3 crystallizes in
the monoclinic crystal system P21/n. The single-crystal X-
ray diffraction study revealed the formation of a two-di-
mensional coordination polymer, constructed by dinuclear
iodo-bridged copper units Cu2(µ2-I)2 linked by the tetrathi-
oether Ge(CH2SPh)4 ligand in a µ-1κ2S,SЈ:2κSЉ:3κSٞ coor-
dination mode. This arrangement is similar to that of the
tetrathioether ligand Sn(CH2SMe)4 in the 1D coordination
polymer [{{Sn(CH2SMe)4}(ZnCl2)2}n] [17a]. Each cop-
per(I) ion of the central dimeric Cu2I2 motif possesses a
fourfold coordination to two iodine and two sulfur atoms,
respectively, resulting in a distorted tetrahedral geometry.
Interestingly, both copper(I) ions of this motif are differ-
ently coordinated by the thioether ligand 1b. Whereas Cu(1)
is ligated by two sulfur atoms of a single ligand molecule,
Cu(2) is coordinated by two different ligands 1b, which
are linked to the metal ion with only one sulfur atom
(Figure 3, Table 2). The CuϪS bond lengths
I(1)ϪCu(1)ϪI(2)
I(1)ϪCu(2)ϪI(2)
Cu(1)ϪI(1)ϪCu(2)
Cu(1)ϪI(2)ϪCu(2)
111.65(3)
110.62(3)
67.39(2)
68.96(3)
˚
work. A somewhat closer contact of 2.862(2) A was found
in the dinuclear compound [{MeSi(CH2SMe)3}CuI]2 [11b].
A distance of 2.8058(11) A, which is close to the sum of
˚
˚
the van der Waals radii of two copper atoms (2.8 A) was
encountered in the 2D metallopolymer [{(CuI)2{(µ-
PhS(CH2)2)SPh}}n] [28a]. According to a survey of the
Cambridge Structural Database, the mean value established
for a variety of [Cu(µ-I)2Cu] complexes amounts to
˚
ϳ 2.76 A [11b]. An example in the short range is given by
a SMe2-functionalized tetrathiafulvalene dinuclear Cu2I2
complex with a metal-metal separation of only 2.65 A [14].
˚
As illustrated in Figure 4, the 2D network of 3 consists
of centrosymmetric 32-membered metallomacrocycles (con-
structed by four ligands and four Cu2I2 units) connected by
centrosymmetric 12-membered rings. The latter cycles are
constituted by two Cu(2) atoms which are linked by two
bridging 1b ligands. Further details of the crystal data and
experimental parameters are presented in Table 3.
Table 3. Crystallographic data and details of the structure determi-
nation of 2b and 3.
2b
3
˚
[2.3378(10)Ϫ2.3731(13) A] are close to those of related
Empirical formula
Formula weight
Crystal system
Space group
C28H28Br2GeHgS4 C28H28Cu2GeI2S4
925.74
polymeric networks found in the literature. The Cu···Cu
946.21
˚
separation of 2.9433(9) A reveals a quite loose non-bonding
triclinic
monoclinic
P21/n
14,628(3)
14.452(3)
15.883(3)
90
107.70(3)
90
3198.7(11)
4
interaction between the two d10 ions in this polymeric net-
¯
P1
˚
a /A
9.437(5)
13.364(5)
13.920(5)
62.08(4)
89.78(6)
79.63(6)
1519.2(12)
2
˚
b /A
˚
c /A
Ͱ /°
β /°
γ /°
3
˚
Cell volume /A
Z
Density (calculated), Mg·mϪ3
F(000)
2.024
884
1.965
1824
Size for single crystal /mm
0.2 ϫ 0.2 ϫ 0.2
0.4 ϫ 0.4 ϫ 0.2
4.460
Absorption coefficient µ /mmϪ1 2.024
Theta range for data collection /° 2.20 to 26.00
2.27 to 27.00
Ϫ18 Յ h Յ 18
Ϫ18 Յ k Յ 18
Ϫ20 Յ l Յ 20
27045
Index range
Ϫ11 Յ h Յ 11
Ϫ16 Յ k Յ 16
Ϫ17 Յ l Յ 17
14275
Reflections collected
Independent reflections
5604
6927
[R(int) ϭ 0.0399] [R(int) ϭ 0.0337]
Goodness of fit on F2
1.015
1.050
Final R indices [I > 2σ(I)]
R1 ϭ 0.03035
wR2 ϭ 0.0694
R1 ϭ 0.0374
wR2 ϭ 0.0714
R1 ϭ 0.0304
wR2 ϭ 0.0806
R1 ϭ 0.0349
wR2 ϭ 0.0834
R indices (all data)
Figure 3. View of the core motif of [{{Ge(CH2SPh)4}(Cu2I2)}n] (3).
The hydrogen atoms and phenyl groups are omitted for clarity.
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Crystal Structures of [{{Ge(CH2SPh)4}HgBr2}n] and [{{Ge(CH2SPh)4}(Cu2l2}}n]
Figure 4. View on the a,b plane of the 2D sheet-like network of [{{Ge(CH2SPh)4}(Cu2I2)}n] (3). Hydrogen atoms and phenyl groups are
omitted for clarity.
Spectroscopic Properties of 1 and 3
is shifted to higher wavelength compared to the emission
The UV/Vis absorption spectra of the tetrathioether observed in CH2Cl2. This emission is comparable with that
ligands 1a and 1b display both a maximum at 259 (ε ϭ observed for other dithioether ligands under similar con-
15600) and 261 nm (ε ϭ 14700 Ϫ1 ·cmϪ1), respectively. ditions, originating probably from the excimer. The struc-
These bands can be attributed to a mixture of πǞπ* and tureless emission band observed of 1b in solid state at 77 K
nǞπ* transitions. After excitation at 260 nm of 1a and 1b was not shifted and revealed no temperature dependence of
in dichloromethane solution at room temperature (Figure the wavelength emission, i.e. no change of the energy for
5), the emission maxima are observed at 341 and 333 nm, the emitting excited state. Unfortunately, the emission exhi-
respectively. These fluorescence bands can be assigned to bited by polymer 3 in solid state at 298 K (Figure 7) is only
the lowest energy singlet state S1ǞS0 transition. Fluor- moderate in intensity, and is most probably due to an
escence quantum yields for 1a (Φ ϭ 0.08) and for 1b (Φ ϭ emission centered on the ligand 1b (LC). It seems that the
0.12) were determined using cresyl violet (Φ ϭ 0.54) as a important Cu···Cu separation, which is far above of sum of
fluorescence quantum yield standard [33]. Upon irradiation the van der Waals radii, excludes other excited state contri-
at 380 nm, compound 1b exhibits in the solid state at 298 K bution such as CC or XMLCT (i.e. cluster-centered or
an emission with a maximum at 440 nm (Figure 6), which halide-to-metal-to-ligand charge transfer).
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H. N. Peindy, F. Guyon, A. Khatyr, M. Knorr, V. H. Gessner, C. Strohmann
ARTICLE
Figure 7. Normalized solid-state excitation (solid line) and emission
(dotted line) spectra of 3 recorded at 298 K.
Figure 5. Normalized emission spectra recorded for 1a (solid line)
and 1b (dotted line) in CH2Cl2 at 298 K.
1
is based on elemental analyses and the H-NMR spectrum,
which displays a singlet at δ ϭ 2.70 for the four methylene
protons of the pendent CH2SPh arms and two low-field
shifted AX resonances at δ ϭ 2.74 and 3.79 assigned to the
diastereotopic CH2 groups of the rhenium-bound CH2SPh
arms. The observation of three strong ν(CO) vibrations cor-
roborates the facial geometry of the three carbonyls around
rhenium. Overall, the molecular structure of 4 is likely very
similar to that of the structurally characterized chelate com-
plex fac-[ReBr(CO)3{(PhSCH2)2SiPh2}] [21].
Conclusions
We have demonstrated that, unlike C(CH2SPh)4, the
tetrathioether germane Ge(CH2SPh)4 coordinates to HgBr2
and that the resulting metallopolymer 2b displays a one-
dimensional extended structure in the crystalline state. The
intermolecular HgϪS contacts in 2b are markedly weaker
than the intramolecular ones. In the case of CuI, a 2D poly-
mer of composition [{Ge(CH2SPh)4}(Cu2I2)]n (3) is formed
upon reaction with 1b in a 2:1 metal-to-ligand ratio. The
Figure 6. Normalized solid-state excitation (solid line) and emission
(dotted line) spectra of 1b recorded at 298 K.
Synthesis of [ReBr(CO)3{Ge(CH2SPh)4}] (4)
For comparison, we also reacted 1b with the dinuclear presence of two pendent CH2SPh arms in the mononuclear
compound [{Re(µ-Br)(CO)3(THF)}2] in CH2Cl2 solution chelate compound fac-[ReBr(CO)3{Ge(CH2SPh)4}] (4) ap-
at ambient temperature. IR monitoring showed, that pears promising to construct heterometallic systems by
within 1 h quantitative cleavage of the bromide bridges complexation of other metal ions on the two non-coordi-
occurred affording the mononuclear compound fac- nated ϪSPh groups. Our ongoing systematic studies on the
[ReBr(CO)3{Ge(CH2SPh)4}] (4) in 76 % yield in form of an coordination chemistry of Si(CH2SAr)4 and Ge(CH2SPh)4
air-stable colorless solid (Scheme 2). In this chelate com- towards other copper, silver and mercury salts and various
plex, two CH2SPh arms are ligated on ReI, the remaining carbonyl compounds will be published elsewhere in the
two CH2SPh arms are dangling. This structural proposition near future.
Scheme 2. Preparation of the mononuclear ReI carbonyl complex 4.
2104
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 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 2099Ϫ2105

Crystal Structures of [{{Ge(CH2SPh)4}HgBr2}n] and [{{Ge(CH2SPh)4}(Cu2l2}}n]
27, 5394; c) H. Gilman, L. F. Cason, J. Brooks, J. Am. Chem.
Soc. 1953, 75, 3760.
Acknowledgement
[16] R. D. Brasington, R. C. Poller, J. Organomet. Chem. 1972,
40, 115.
We are grateful to the Deutsche Forschungsgemeinschaft, the Bayer-
[17] a) K. Ruth, M. Müller, M. Bolte, J. W. Bats, M. Wagner,
H.-W. Lerner, Z. Anorg. Allg. Chem. 2007, 633, 1485; b) The
homoleptic complex [Li2Ni(CH2SPh)4] x Et2O has been pre-
pared by Steinborn et al.: F. Becke, T. Rüffer, R. Boese, D.
Bläse, D. Steinborn, J. Organomet. Chem. 1997, 545Ϫ546, 169.
[18] C. Strohmann, E. Wack, Z. Naturforsch. 2004, 59b, 1570.
[19] F. Calderazzo, I. P. Mavani, D. Vitali, I. Bernal, J. D. Korp, J.
L. Atwood, J. Organomet. Chem. 1978, 160, 207.
[20] a) G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467; b)
G. M. Sheldrick, SHELX97, Program for Refinement of Crys-
tal Structures, Göttingen 1997.
`
isch-Französisches Hochschulzentrum and the French Ministere de
´
l’Enseignement Superieur et de la Recherche for financial support.
Financial support from the Region of Franche-Comte for the fluor-
´
´
escence spectrometer is also gratefully acknowledged.
References
[1] a) M. Gingras, J.-M. Raimundo, Y. M. Chabre, Angew. Chem.
Int. Ed. 2006, 45, 1686; b) L. A. Lucas, D. M. DeLongchamp,
L. J. Richter, R. J. Kline, D. A. Fischer, B. R. Kaafarani, G.
E. Jabbour, Chem. Mater. 2008, 20, 5743.
[2] a) A. Bastero, C. Claver, A. Ruiz, Catal. Lett. 2002, 82, 85.
[3] a) M. M. Maye, S. C. Chun, L. Han, D. Rabinovich, C.-J.
Zhong, J. Am. Chem. Soc. 2002, 124, 4958; b) T. Weidner, A.
Kraemer, C. Bruhn, M. Zharnikov, A. Shaporenko, U. Sieme-
ling, F. Traeger, Dalton Trans. 2006, 2767.
[4] a) Y.-T. Fu, V. M. Lynch, R. J. Lagow, Chem. Commun. 2003,
1069; b) M. O. Awaleh, F. Baril-Robert, C. Reber, A. Badia, F.
Brisse, Inorg. Chem. 2008, 47, 2964.
[5] a) J.-R. Li, X.-H. Bu, Eur. J. Inorg. Chem. 2008, 27; b) S. Ferley,
A. Jouaiti, M. Lo¨ı, M. W. Hosseini, A. De Cian, P. Turek, New
J. Chem. 2003, 27, 1801.
[6] C. Strohmann, S. Lüdtke, E. Wack, Chem. Ber. 1996, 129, 799.
[7] C. Strohmann, S. Lüdtke, O. Ulbrich, Organometallics 2000,
19, 4223.
[8] a) M. Knorr, S. Kneifel, C. Strohmann, in Organosilicon Chem-
istry III: From Molecules to Materials, Eds.: N. Auner, J. Weis;
Wiley-VCH, Weinheim, 1998, pp. 211Ϫ216; b) M. Knorr, F.
Guyon, I. Jourdain, S. Kneifel, J. Frenzel, C. Strohmann, Inorg.
Chim. Acta 2003, 350, 455.
[9] M. Knorr, H. N. Peindy, F. Guyon, H. Sachdev, C. Strohmann,
Z. Anorg. Allg. Chem. 2004, 630, 1955.
[10] H. N. Peindy, F. Guyon, I. Jourdain, M. Knorr, D. Schildbach,
C. Strohmann, Organometallics 2006, 25, 1472.
[21] D. C. Goodall, J. Chem. Soc. 1967, 1387.
[22] Concerning the somewhat related selenoether complexes
[(Me3SiCH2SeMe)HgX2]2 see: R. K. Chadha, J. E. Drake, N.
T. McManus, A. Mislankar, Can. J. Chem. 1987, 65, 2305.
[23] A. J. Blake, W. Li, V. Lipolis, A. Taylor, M. Schröder, J. Chem.
Soc., Dalton Trans. 1998, 2931.
[24] M. Herceg, D. Matkovic-Calogovic, Acta Crystallogr., Sect. C
1992, 48, 1779.
[25] M. Knorr, H. N. Peindy, F. Guyon, H. Sachdev, C. Strohmann,
Z. Anorg. Allg. Chem. 2005, 631, 2397.
[26] J.-B. Gong, L.-N. Zhou, W. Chen, Acta. Crystallogr., Sect. E
2006, 62, m440.
[27] For other examples of mono-dimensional HgII coordination
polymers see: a) A. Hameau, F. Guyon, M. Knorr, M. Enescu,
C. Strohmann, Monatsh. Chem. 2006, 137, 545; b) G. Mah-
moudi, A. Morsalia, M. Zeller, Solid State Sci. 2008, 10, 283;
c) X.-P. Li, J.-Y. Zhang, Y. Liu, M. Pan, S.-R. Zheng, B.-S.
Kang, C.-Y. Su, Inorg. Chim. Acta 2007, 10, 2990; d) P. Nocke-
mann, G. Meyer, Acta Crystallogr., Sect. E 2004, 60, m747; e)
R. S. Mc Ewen, G. A. Sim, J. Chem. Soc. A 1969, 1897; f) J.
E. Fiscus, N. Pschirer, R. E. Hipp, A. M. Goforth, C. Chap-
man, S. Shotwell, R. C. Layland, M. D. Smith, U. H. F. Bunz,
H.-C. zur Loye, J. Chem. Crystallogr. 2005, 35, 125.
[28] a) H. N. Peindy, F. Guyon, A. Khatyr, M. Knorr, C.
Strohmann, Eur. J. Inorg. Chem. 2007, 1823; b) M. Knorr, F.
Guyon, A. Khatyr, C. Däschlein, C. Strohmann, S. M. Aly, A.
S. Abd-El-Aziz, D. Fortin, P. D. Harvey, Dalton Trans. 2009,
948.
[29] a) H. D. Hardt, A. Pierre, J. Bourassa, Z. Anorg. Allg. Chem.
1973, 402, 107; b) E. Eitel, D. Oelkrug, W. Hiller, J. Strähle, Z.
Naturforsch. 1980, 35b, 1247; c) G. Hu, G. J. Mains, E. M.
Holt, Inorg. Chim. Acta 1995, 240, 559.
[30] P. C. Ford, E. Cariati, J. Bourassa, Chem. Rev. 1999, 99, 3625.
[31] N. Armaroli, G. Accorsi, F. Cardinali, A. Listorti, Top. Curr.
Chem. 2007, 280, 69.
[11] a) H. W. Yim, L. M. Tran, E. E. Pullen, D. Rabinovich, L. M.
Liable-Sands, T. E. Concolino, A. L. Rheingold, Inorg. Chem.
1999, 38, 6234; b) H. W. Yim, D. Rabinovich, K.-C. Lam, J.
A. Golen, A. L. Rheingold, Acta Crystallogr., Sect. E 2003,
59, 556.
[12] H. W. Yim, K.-C. Lam, A. L. Rheingold, D. Rabinovich, Poly-
hedron 2000, 19, 849.
[13] W. C. Blackwell-III, D. Bunich, T. E. Concolino, A. L. Rhein-
gold, D. Rabinovich, Inorg. Chem. Commun. 2000, 3, 325.
[14] W. Lu, Z.-M. Yan, J. Dai, Y. Zhang, Q.-Y. Zhu, D.-X. Jia,
W.-J. Guo, Eur. J. Inorg. Chem. 2005, 2339.
[15] a) H. N. Peindy, F. Guyon, M. Knorr, A. B. Smith, J. A.
Farouq, S. A. Islas, D. Rabinovich, J. A. Golen, C. Strohmann,
Inorg. Chem. Commun. 2005, 8, 479; b) a series of Si(CH2SR)4
derivatives has recently been prepared by hydrothiolation of
Si(CHϭCH2)4: C. Rissing, D. Y. Son, Organometallics 2008,
[32] T. H. Kim, K. Y. Lee, Y. W. Shin, S.-T. Moon, K.-M. Park, J.
S. Kim, Y. Kang, S. S. Leea, J. Kim, Inorg. Chem. Commun.
2005, 8, 27.
[33] D. Magde, J. H. Brannon, T. L. Cremers, J. Olmsted, J. Phys.
Chem. 1979, 83, 696.
Received: January 4, 2009
Published Online: April 8, 2009
Z. Anorg. Allg. Chem. 2009, 2099Ϫ2105
 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2105