Binary and ternary cluster complexes containing gold-selenium, gold-indium-selenium and gold-gallium-tellurium

Article abstract of DOI:10.1002/ejic.200300774

Reactions of gold phosphane complexes [(AuX)(PR₃)] (X = Cl, Br, I; R = organic moiety) with Se(SiMe₃)₂ lead to the formation of gold complexes with chalcogenide bridges. The reaction of the complex [Ph₃PAuCl] and tBuSe(SiMe₃) gives the cluster [Au₅Se₂(PPh₃)₄]Cl (1). The in situ preparation of the complex [(AuCl)₂dpph] [dpph = Ph ₂P(CH₂)₆PPh₂] by reaction of dpph with [Me₂SAuCl], and subsequent reaction with Se(SiMe ₃)₂, leads to the formation of [(Au₃Se) ₂(dpph)₃]Cl₂ (2). Reactions of the gold(I) complex [(AuCl)₂dpppe] [dpppe = Ph₂P(CH₂) ₅PPh₂] with Se(SiMe₃)₂ and InCl ₃ in different molar ratios lead to the formation of [Au ₁₀Se₄(dpppe)₄]InCl₅ (3) and [Au ₄(SeInCl₃)₂(dpppe)₂] (4). The reaction of [(AuCl)₂dpph] with Te(SiMe₃)₂ and GaCl₃ produces the isostructural cluster compound [Au ₄(TeGaCl₃)₂(dpph)₂] (5). From the reaction of Se(SiMe₃)₂ with [(AuCl)₂dppe] [dppe = Ph₂P(CH₂)₂PPh₂] and InCl ₃ [Au₈Se₄In(dppe)₄](InCl ₄)₃ 6 can be isolated. The structures of 1-6 were determined by X-ray diffraction. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300774

FULL PAPER
Binary and Ternary Cluster Complexes Containing Gold-Selenium, Gold-
Indium-Selenium and Gold-Gallium-Tellurium ؊ Synthesis and Structures of
[Au5Se2(PPh3)4]Cl, [(Au3Se)2{Ph2P(CH2)6PPh2}3]Cl2,
[Au10Se4{Ph2P(CH2)5PPh2}4]InCl5, [Au4(SeInCl3)2{Ph2P(CH2)5PPh2}2],
[Au2(TeGaCl3){Ph2P(CH2)6PPh2}]2 and [Au8Se4In{Ph2P(CH2)2PPh2}4](InCl4)3
Jolanta Olkowska-Oetzel,[a] Paloma Sevillano,[b] Andreas Eichhöfer,[c] and
Dieter Fenske*[a,b,c]
Keywords: Cluster compounds / Gallium / Gold / Indium / Selenium / Tellurium
Reactions of gold phosphane complexes [(AuX)(PR3)] (X = Cl,
molar ratios lead to the formation of [Au10Se4(dpppe)4]InCl5
Br, I; R = organic moiety) with Se(SiMe3)2 lead to the forma- (3) and [Au4(SeInCl3)2(dpppe)2] (4). The reaction of
tion of gold complexes with chalcogenide bridges. The reac-
tion of the complex [Ph3PAuCl] and tBuSe(SiMe3) gives the
cluster [Au5Se2(PPh3)4]Cl (1). The in situ preparation of the
complex [(AuCl)2dpph] [dpph = Ph2P(CH2)6PPh2] by reaction
[(AuCl)2dpph] with Te(SiMe3)2 and GaCl3 produces the isos-
tructural cluster compound [Au4(TeGaCl3)2(dpph)2] (5). From
the reaction of Se(SiMe3)2 with [(AuCl)2dppe] [dppe =
Ph2P(CH2)2PPh2] and InCl3 [Au8Se4In(dppe)4](InCl4)3 6 can
of dpph with [Me2SAuCl], and subsequent reaction with Se(- be isolated. The structures of 1−6 were determined by X-
SiMe3)2, leads to the formation of [(Au3Se)2(dpph)3]Cl2 (2).
ray diffraction.
Reactions of the gold( ) complex [(AuCl)2dpppe] [dpppe =
I
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Ph2P(CH2)5PPh2] with Se(SiMe3)2 and InCl3 in different
Germany, 2004)
Introduction
kind of preparations, using silylated derivatives of S, Se and
Te, were reported by Abel et al. and Schmidbaur et al.[9]
The use of polyphosphanes leads to the formation of
large cluster complexes containing copper[10] and silver[11]
atoms bridged by chalcogenides. Polyphosphanes were also
successfully applied in analogous reactions with gold()
salts, resulting in the formation of several gold cluster com-
plexes which have been characterized, for example [Au18-
Se8(dppe)6]Br2,[12] [Au10Se4(dpppe)4]Br2,[13] [Au34Se14(tpep)6-
Due to the important photophysical and photochemical
properties of gold() complexes, many investigations have
been undertaken towards the synthesis and structural
analysis of gold complexes and clusters.[1Ϫ5] However, only
a few examples of gold complexes with selenium or tel-
lurium bridges are known.[2,6]
For the preparation of this kind of cluster complex, a
reaction has been developed using metal halides MXn (M ϭ
metal; X ϭ Cl, Br, I) and silylated main group element de-
rivatives, RϪEϪSiMe3 (R ϭ organic group, SiMe3; E ϭ S,
Se, Te), in the presence of a tertiary phosphane PR3. The
driving force of this reaction is the formation of the corre-
sponding trimethylsilyl halide, XSiMe3.[7] The phosphane
ligands stabilize the metal cluster complex and avoid
theformation of the binary phases.[8] The first results in this
(tpepSe)2]Cl6 [tpep ϭ P(PCH2CH2PPh3)3 and tpepSe
ϭ
Ph2P(Se)CH2CH2P(PCH2CH2PPh3)2].[14] Some have been
found to have luminescent properties, for example [Au10-
Se4(dpppe)4]Br2,[13] [Au10(µ3-S)4(PNP)4][PF6]2 [PNP
ϭ
Ph2PN(Pr)PPh2][15] and [Au12Se4(dppm)6](PF6)4 (dppm ϭ
Ph2PCH2PPh2).[16]
In contrast to the well-known binary chalcogenide cluster
complexes of group 11 metals,[17,18] ternary chalcogenide
compounds containing metals of group 11 and 13 are rare
and of special interest due to their promising properties.
For example, the ternary compounds CuInSe2 or CuGaSe2
have important potential in thin film technology for solar
cells.[19] Recently, some ternary cluster compounds, for ex-
ample [Cu11In15Se16(SePh)24(PPh3)4],[20] [Cu6In8S13Cl4-
(PEt3)12][21] and [Ag6In8S13Cl4(PPh3)12][22] have been syn-
thesized. Ternary In-Au and Ga-Au chalcogenide cluster
[a]
DFG Center for Functional Nanostructures (CFN)
Universität Karlsruhe
76128 Karlsruhe, Germany
Fax: (internat.) ϩ49-721-608-8440
E-mail: Dieter.Fenske@chemie.uni-karlsruhe.de
[b]
Institut für Anorganische Chemie der Universität Karlsruhe
76128 Karlsruhe, Germany
[c]
Institut für Nanotechnologie im Forschungszentrum Karlsruhe
76128 Karlsruhe, Germany
1100
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New Binary and Ternary Cluster Complexes
FULL PAPER
Scheme 1. Preparation reactions of compounds 1Ϫ6
compounds have, to the best of our knowledge, not yet cussed. Two molecules of dichloromethane are present as
been prepared.
lattice-bound solvent in the crystal.
In this work we report the preparation and X-ray charac-
terization of some Au-chalcogenide, In-Au and Ga-Au chal-
cogenide cluster compounds.
Results and Discussion
Compounds 1؊6 were prepared as shown in Scheme 1.
From the reaction of [Ph3PAuCl] with tBuSe(SiMe3) in
CH2Cl2 at room temperature a pale yellow solution was ob-
tained. Layering of the solution with n-pentane produced
yellow crystals of [Au5Se2(PPh3)4]Cl (1). Crystals of the
compound
[(Au3Se)2(dpph)3]Cl2
[2;
dpph
ϭ
Ph2P(CH2)6PPh2] were obtained from the reaction of the
corresponding phosphane ligand with [Me2SAuCl] and
Se(SiMe3)2 in CH2Cl2. The final yellow solution was lay-
ered with n-pentane and, after a few days, yellow crystals
were isolated.
Reaction of the gold() complex [(AuCl)2dpppe] [dpppe ϭ
Ph2P(CH2)5PPh2][23] with two equivalents of Se(SiMe3)2
and one equivalent of InCl3 in CH2Cl2/THF gave the for-
mation of small yellow crystals of 3. If the reaction is car-
ried out using an Se:In molar ratio of 1:2, cubic crystals of
4 are formed. Colorless crystals of the isostructural cluster
Figure 1. Crystal structure of the cation in 1; selected distances
(pm) and angles (°): Au1ϪAu2 305.94(9), Au2ϪAu3 299.56(10),
Au3ϪAu4 304.87(10), Au3ϪAu5 327.04(11), Au1ϪSe1 245.17(12),
Au2ϪSe1 245.58(14), Au3ϪSe1 246.43(12), Au3ϪSe2 245.75(12),
Au4ϪSe2 243.48(14), Au5ϪSe2 243.83(12), Au1ϪP1 227.4(2),
Au2ϪP2 226.6(3), Au4ϪP4 226.4(3), Au5ϪP5 226.6(3);
Au1ϪSe1ϪAu2 77.13(4), Au1ϪSe1ϪAu3 78.64(4), Au2ϪSe1ϪAu3
75.01(4), Au4ϪSe2ϪAu5 79.89(4), Au4ϪSe2ϪAu3 77.09(4),
Au5ϪSe2ϪAu3 83.82(4), Se2ϪAu3ϪSe1 177.87(4), P1ϪAu1ϪSe1
171.15(7), P2ϪAu2ϪSe1 167.65(7), P4ϪAu4ϪSe2 170.93(7),
P5ϪAu5ϪSe2 170.27(7)
The Au5Se2 units in 1 are composed of two Au3Se tetra-
hedra which share a corner; there are no bonds between
the gold atoms inside the Au5Se2 unit (see Figure 1). The
observed AuϪAu distances are within the range
299.56(10)Ϫ327.04(11) pm. All selenium atoms act as µ3-
bridges above and below the plane defined by the gold
atoms Au1 to Au5, with AuϪSeϪAu angles between
75.01(4)° and 83.82(4)°. AuϪSe distances range from
243.48(14) to 246.43(12) pm, and are within the range of
commonly observed distances in other AuϪSe cluster
compound
5 were obtained from the reaction of
[(AuCl)2dpph] with Te(SiMe3)2 and GaCl3 in CH2Cl2/THF,
and from the reaction of Se(SiMe3)2 with [(AuCl)2dppe]
[dppe ϭ Ph2P(CH2)2PPh2] and InCl3 (1:1:1) in CH2Cl2/
THF colorless needles of 6 could be isolated.
The structures of the six compounds were determined by
single-crystal X-ray crystallography.
[Au5Se2(PPh3)4]Cl (1)
Complex 1 crystallizes in the triclinic space group P1 complexes.[12Ϫ16]
¯
with four molecules per unit cell and two molecules per
The central gold atom has an almost linear coordination
asymmetric unit (Figure 1). These are identical within the to two selenium atoms (Se1, Se2) with an angle of
standard deviations therefore only one of them will be dis- 177.87(4)°. The peripheral gold atoms also show a linear
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J. Olkowska-Oetzel, P. Sevillano, A. Eichhöfer, D. Fenske
FULL PAPER
coordination geometry. The SeϪAuϪP angles are between 175.10(7)Ϫ177.58(7)° and the AuϪP distances are between
167.65(7) and 171.15(7)°, and the AuϪP distances range 226.2(2) and 227.6(3) pm.
from 226.4(3) to 227.4(2) pm. An isostructural compound
[Au{S(AuPPh3)2}2][(CH3)3SnCl2], prepared using a differ- distances range from 301.66(8) to 326.19(10) pm. The inter-
ent procedure, has already been reported by Jones et al.[24]
molecular AuϪAu distances between two Au3Se units are
Au5Se2 units are known building blocks in other AuϪSe relatively short, with a value of 304.27(7) pm. This shows
Within the Au3Se tetrahedra, the non-bonding AuϪAu
cluster cations. Some examples are [Au10Se4(dppm)4]2ϩ
[Au10Se4(dpppe)4]2ϩ and [Au10Se4(depe)4]2ϩ [depe
,
ϭ
that the short interactions, probably due to the ‘‘aurophilic
attraction’’, lead to the formation of a polymeric chain of
Et2P(CH2)2PEt2].[13,14] In these cases, the complex cations cations in the solid state.[25] Other examples of gold cluster
are formed by two Au5Se2 units bridged by the phosphane complexes with secondary AuϪAu bonding and solid-state
ligands. In the complexes containing dppm and depe, the polymers can be found in the literature.[14,26,27]
phosphane carbon chains are shorter, resulting in the for-
[Au10Se4(dpppe)4]InCl5 (3)
mation of more-distorted Au3Se tetrahedra. In the case of
dpppe, the phosphane bridge is longer, resulting in an al-
most regular Au3Se tetrahedron. In 1, however, where a
monodentate phosphane ligand was used for the prep-
aration, almost regular Au3Se tetrahedra are observed as
there is no distortion due to the formation of bridges (see
above).
Complex 3 crystallizes in the monoclinic space group C2/
c with four molecules per unit cell. The Au5Se2 units within
the cation of 3 are bridged by dpppe ligands (see Figure 3).
The AuϪAu distances between the Au5Se2 units are
312.3(2) and 333.2(2) pm. The Au5Se2 units consist of two
Au3Se tetrahedra sharing a corner (see above). In these
tetrahedra, the selenium atoms are acting as µ3-bridges to
three gold atoms, being placed above and below the plane
formed by the gold atoms (Au1ϪAu5 and symmetry equiv-
alents) with AuϪSeϪAu angles of 74.02(9)° and 82.61(8)°.
The AuϪSe distances range between 245.2(3) and 247.4(3)
pm (Figure 3).
[(Au3Se)2(dpph)3]Cl2 (2)
Complex 2 crystallizes in the monoclinic space group
P21/c with four molecules per unit cell. One molecule of n-
pentane and one of dichloromethane are present as lattice-
bound solvent in the crystal. The bond lengths and angles
are within the expected range.[12Ϫ16] The cation
[(Au3Se)2(dpph)3]2ϩ is composed of two Au3Se tetrahedra
bridged by dpph ligands (see Figure 2).
Figure 2. Crystal structure showing two cations in 2; phenyl rings
are omitted for clarity; symmetry transformations for the genera-
tion of equivalent atoms: Ϫx ϩ 1, Ϫy ϩ 1, Ϫz ϩ 1; selected dis-
tances (pm) and angles (°): Au1ϪAu2 326.19(10), Au1ϪAu3
301.66(8) Au2ϪAu3# 304.27(7), Au3ϪAu2# 304.27(7), Au1ϪSe1
242.47(10), Au2ϪSe1 245.38(11), Au3ϪSe1 247.35(11), Au1ϪP1
226.2(2), Au2ϪP2 227.6(3), Au3ϪP3 227.3(2); P1ϪAu1ϪSe1
175.10(7), P2ϪAu2ϪSe1 176.10(9), P3ϪAu3ϪSe1 177.58(7),
Figure 3. Crystal structure of 3; symmetry transformations for the
generation of equivalent atoms: Ϫx ϩ 1, y, Ϫz ϩ 1/2; selected dis-
tances (pm) and angles (°): Au1ϪSe2 244.9(3), Au1ϪAu3
302.32(16), Au1ϪAu1Ј 312.3(2), Au1ϪAu5 323.47(19), Au2ϪSe1
247.4(3), Au2ϪAu3 294.72(14), Au3ϪSe1 242.2(3), Au3ϪSe2
242.7(3), Au3ϪAu5 306.18(15), Au3ϪAu4 328.29(16), Au4ϪP3Ј
225.6(8), Au4ϪSe1 244.5(3), Au4ϪAu2Ј 314.27(18), Au5ϪP1
226.4(7), Au5ϪSe2 245.2(3), Au5ϪAu5Ј 333.2(2); P4ϪAu1ϪSe2
171.9(2), P4ϪAu1ϪAu1Ј 108.9(2), Se2ϪAu1ϪAu1Ј 78.70(7),
Au1ϪSe1ϪAu3
Au3ϪAu2ϪAu1
Au3#ϪAu2ϪAu3
76.02(3),
55.18(2),
84.98(2),
Au2ϪSe1ϪAu3
Au3ϪAu1ϪAu2
Au3#ϪAu2ϪAu1
82.58(3),
62.23(2),
124.55(1),
Au1ϪAu3ϪAu2# 135.04(2), Au2#ϪAu3ϪAu2 95.02(2)
Au3ϪAu1ϪAu1Ј
Se2ϪAu1ϪAu5
Au3ϪAu2ϪAu4
Au2ϪAu3ϪAu1
Se2ϪAu5ϪAu1
130.03(4),
48.73(7),
64.92(4),
160.88(5),
48.66(8),
P4ϪAu1ϪAu5
Au3ϪAu1ϪAu5
Se1ϪAu3ϪSe2
P1ϪAu5ϪAu1
Au3ϪAu5ϪAu1
132.0(2),
58.47(4),
175.17(9),
131.6(2),
57.31(4),
Selenium atoms act as µ3-bridges to three gold atoms,
building slightly distorted Au3Se tetrahedra. The SeϪAu
distances are between 242.47(10) and 247.35(11) pm, and
the AuϪSeϪAu angles range from 76.02(3) to 82.58(3)°.
All gold atoms exhibit an almost linear coordination ge-
Au3ϪSe1ϪAu2 74.02(9), Au1ϪSe2ϪAu5 82.61(8)
A distorted linear coordination geometry is found for the
ometry and are coordinated by a phosphorus and a sel- central gold atom (Au3 and symmetry equivalents), bonded
enium atom. The PϪAuϪSe angles are within the range to two selenium atoms with an SeϪAuϪSe angle of
1102
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New Binary and Ternary Cluster Complexes
FULL PAPER
175.17(9)° and AuϪSe distances of 242.2(3) and 242.7(3) below the plane of the four-membered ring of gold atoms
pm. All non-central gold atoms also display a linear ge- (Au1ϪAu2ϪAu1ЈϪAu2Ј) with an Au1ЈϪSe1ЈϪAu2 angle
ometry and are coordinated to a selenium and a phos- of 78.83(3)°. With the InCl3 directly bonded to the selenium
phorus atom, with AuϪP bond lengths between 225.6(8) atom, compound 4 represents the first step in the build-up
and 227.7(7) pm and PϪAuϪSe angles ranging from of ternary gold indium chalcogenide complexes.
169.06(8)° to 175.28(19)°.
[Au2(TeGaCl3)dpph]2 (5)
An isostructural cation was found in the complex [Au10-
Se4(dpppe)4]Br2.[13,14] However, the AuϪAu distances be-
tween the Au5Se2 units in 3 [312.3(2) and 333.2(2) pm] are
longer than those in [Au10Se4(dpppe)4]Br2 [300.2(3) and
326.0(4) pm]. The AuϪAu distances within the Au5Se2 units
are shorter in 3 [range from 294.7(30) to 328.3(8) pm] than
the ones found in the isostructural cluster [Au10-
Se4(dpppe)4]Br2 [298.0(3) to 334.1(3) pm].
Compound 5 crystallizes in the monoclinic space group
P21/c with two molecules per unit cell. This cluster shows
the same structural motif as 4, with a central arrangement
of four gold atoms, bridged by tellurium atoms, which are
also coordinated to a GaCl3 molecule (see Figure 5). A dis-
torted linear geometry at each of the gold atoms is ob-
served, with PϪAuϪTe angles ranging from 171.45(4)° to
176.42(4)°. The µ3-Te2Ϫ ligands are also coordinated to a
Ga atom (Ga1, Ga1Ј) of a GaCl3 molecule. The AuϪAu
distances are Au1ϪAu2 305.03(9) and Au2ϪAu1Ј 340.8(1)
pm with Au1ϪAu2ϪAu1Ј and Au2ЈϪAu1ЈϪAu2 angles of
92.10(1)° and 87.90(1)°, respectively.
[Au2(SeInCl3)dpppe]2 (4)
¯
Cluster 4 crystallizes in the triclinic space group P1 with
two molecules per unit cell. In 4 two gold atoms (Au1,
Au2Ј) are coordinated to a selenium atom (Se1) and two
phosphorous atoms (P1Ј, P2) of the bidentate phosphane
ligand (see Figure 4), leading to a distorted linear coordi-
nation at gold (PϪAuϪSe from 173.59(4)° to 178.39(4)°].
The µ3-Se2Ϫ ligand is also coordinated to an In atom (In1)
of an InCl3 molecule. In the crystal lattice, two [Au2(Se-
InCl3)dpppe] units form a dimer by inversion symmetry,
with a planar square of gold atoms (Au1ЈϪAu2ϪAu1
83.94(3) and Au2ЈϪAu1ϪAu2 96.06(3)°]. The AuϪAu dis-
tances within the Au2Se units [Au1ϪAu2Ј 320.88(9) pm] are
slightly longer than the ones found between both Au2Se-
units [(Au1ϪAu2 311.67(10) pm]. Related Au4 arrange-
ments have been observed before in the ionic complex
[(PPh3Au)2(SCH2Ph)](NO3), with values of 307.7 and 319.4
pm for the non-bridged AuϪAu distances and distances of
307.7 and 314.2 pm for the bridged ones,[28] and also in
[(PPh3Au)2(SC6H4CH3)2](PF6), which has AuϪAu dis-
tances of 317.3 pm for the free edges and 315.2 pm for the
sulfur-bridged ones.[28] In analogy to these sulfur-bridged
complexes, the selenium atoms in 4 are placed above and
Figure 5. Molecular structure 5; symmetry transformations for the
generation of equivalent atoms: Ϫx ϩ 1, Ϫy ϩ 1, Ϫz; selected
distances (pm) and angles (°): Ga1ϪTe1 258.92(12), Te1ϪAu1
259.43(6), Te1ϪAu2Ј 260.69(6), Au1ϪAu2 305.03(9), Au2ϪP2
228.66(14), Au2ϪTe1Ј 260.69(6); Ga1ϪTe1ϪAu1 93.96(3),
Ga1ϪTe1ϪAu2Ј
88.89(2),
Au1ϪTe1ϪAu2Ј
81.87(2),
P1ϪAu1ϪTe1 171.45(4), P1ϪAu1ϪAu2 107.21(4), Te1ϪAu1ϪAu2
81.34(2), P2ϪAu2ϪTe1Ј 176.42(4), P2ϪAu2ϪAu1 98.32(4),
Te1ЈϪAu2ϪAu1 84.145(19)
[Au8Se4In(dppe)4](InCl4)3 (6)
Compound 6 crystallizes in the monoclinic space group
C2/c (Figure 6). The hydrogen atoms were not calculated
for this crystal structure. One molecule of dichloromethane
is present as lattice-bound solvent in the crystal. The cation
consists of a central indium atom (In1) enclosed within a
distorted tetrahedron of four selenium atoms (Se1, Se2,
Se1Ј, Se2Ј). The InϪSe distances range from 258.5(3) to
259.5(3) pm with SeϪInϪSe angles ranging between
107.10(14)° and 110.85(8)°. Each of these µ3-Se atoms coor-
dinates to two Au atoms (Au1ϪAu4 and symmetry equiva-
lent atoms) forming four Au2Se units with AuϪSe bond
lengths ranging from 244.7(3) to 244.8(3) pm and
AuϪSeϪAu angles within the range 77.12(7)Ϫ78.29(8)°.
All the bidentate phosphane ligands (P1ϪP4 and symmetry
equivalent atoms) bridge two Au atoms belonging to two
different Au2Se units, resulting in a distorted linear coordi-
nation environment for all Au atoms. Each gold atom is
Figure 4. Crystal structure of 4; symmetry transformations for the
generation of equivalent atoms: Ϫx ϩ 2, Ϫy ϩ 1, Ϫz; selected
distances (pm) and angles (°): In1ϪSe1 254.74(11), Se1ϪAu1
244.60(8), Se1ϪAu2Ј 244.95(8), Au1ϪP2 226.07(16), Au1ϪAu2
311.67(10),
Au1ϪAu2Ј
320.88(9),
Au2ϪSe1Ј
244.95(8);
Au1ϪSe1ϪAu2Ј 81.91(3), Au1ϪSe1ϪIn1 93.95(4), P2ϪAu1ϪSe1
173.59(4), P2ϪAu1ϪAu2 100.64(5), Se1ϪAu1ϪAu2 85.61(4),
Se1ϪAu1ϪAu2Ј
P1ϪAu2ϪSe1Ј
49.09(2),
Au2ϪAu1ϪAu2Ј
P1ϪAu2ϪAu1Ј
96.06(3),
130.20(4),
178.39(4),
Au1ϪAu2ϪAu1Ј 83.94(3)
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24 hours. The solvents were removed in vacuo and water (50 mL)
added. The white precipitate was filtered off, washed with water
and Et2O, and dried in vacuo. Yield 70Ϫ85% (dppe 0.62 g, dpppe
0.74 g, dpph 0.80 g).
coordinated by one Se and one P atom [SeϪAuϪP:
167.52(9)Ϫ177.75(18)°; AuϪP: 226.7(6)Ϫ228.2(7) pm]. A
distorted eight-membered ring in the boat conformation is
formed by the Au atoms, with AuϪAu distances ranging
from 301.41(15) (Au3ϪAu4) to 309.04(17) pm (Au4ϪAu1Ј).
A similar AuϪAu distance of 305.1(1) pm is found in
[(PPh3Au)2Se].[29] The structure of the cation in 3 can be
rationalized as an In atom tetrahedrally coordinated by four
dppeAu2Se units, where phosphane ligands connect neigh-
bouring Au2Se units. Similar Au2Se units have been stabil-
ized and crystallized before by the use of either monodent-
ate phosphane ligands like PPh3 in monomeric
[(PPh3Au)2Se][21] or bidentate phosphanes, such as
Ph2PC6H4PPh2 (dppbe), in the polymeric [Au2-
Se(dppbe)]ϱ.[14]
Preparation of [Au5Se2(PPh3)4]Cl (1): tBuSe(SiMe3) (0.02 mL,
0.022 g, 0.107 mmol) was added at room temperature to a solution
of [Ph3PAuCl] (0.10 g, 0.21 mmol) in CH2Cl2 (10 mL),. The final
mixture was stirred for 14 hours to give a light yellow solution.
This solution was layered with n-pentane and, after a few days,
light yellow crystals of 1 had formed (see Table 1). Yield 60%
(0.06 g). C74H48Au5Cl5P4Se2 (2396.6): calcd. C 37.05, H 2.67; found
C 37.17, H 2.71.
Preparation of [(Au3Se)2(dpph)3]Cl2 (2): A solution of [Me2SAuCl]
(19) (0.1 g, 0.35 mmol) in CH2Cl2 (5 mL) was added to a solution
of dpph (0.08 g, 0.18 mmol) in CH2Cl2 (5 mL). The solutions were
stirred for 30 minutes and Se(SiMe3)2 (0.04 mL, 0.039 g,
0.18 mmol) was added to give a yellow solution. This solution was
layered with n-pentane and, a few days later, crystals of 2 had
formed (see Table 1). Yield 40% (0.07 g). C102H96Au6Cl2P6Se2
(2916.9): calcd. C 41.96, H 3.29; found C 41.82, H 3.25.
Preparation of [Au10Se4(dpppe)4]InCl5 (3): Se(SiMe3)2 (0.10 mL,
0.44 mmol) was added to a solution of [(AuCl)2dpppe] (0.20 g,
0.22 mmol) in CH2Cl2 (25 mL) to give a yellow solution. A solution
of InCl3 (0.05 g, 0.22 mmol) in THF (2 mL) was added and a yel-
low precipitate was formed. The solid was filtered off and a few
days later small yellow crystals of 3 were isolated (see Table 1).
Yield 10% (0.02 g). C116H120Au10Cl5InP8Se4 (4339.6): calcd. C
32.11, H 2.79; found C 29.96, H 2.78.
Figure 6. Molecular structure of the cation in 6; symmetry trans-
formations for the generation of equivalent atoms: Ϫx ϩ 1, y, Ϫz
ϩ 0.5; selected distances (pm) and angles (°): Au1ϪP1 228.2(7),
Au1ϪSe1 244.8(3), Au1ϪAu4Ј 309.04(17), Au2ϪP2 226.7(6),
Au2ϪSe2 244.7(3), Au2ϪAu3 305.06(15), Au3ϪP3 227.9(7),
Au3ϪSe2 244.7(3), Au3ϪAu4 301.41(15), Au4ϪP4 227.4(8),
In1ϪSe1 258.5(3), In1ϪSe2 259.5(3); P1ϪAu1ϪSe1 175.7(2),
P1ϪAu1ϪAu2 92.62(19), Se1ϪAu1ϪAu2 91.61(7), P1ϪAu1ϪAu4Ј
125.01(19), Se1ϪAu1ϪAu4Ј 50.85(7) Au2ϪAu1ϪAu4Ј 137.92(5),
P2ϪAu2ϪSe2 167.52(19), P2ϪAu2ϪAu1 92.49(18), Se1ϪIn1ϪSe2
110.85(8), Se2ϪIn1ϪSe2Ј 107.10(14), Au4ЈϪSe1ϪAu1 78.29(8),
Au4ЈϪSe1ϪIn1 97.73(9)
Preparation of [Au4(SeInCl3)2(dpppe)2] (4): Se(SiMe3)2 (0.05 mL,
0.22 mmol) was added to a solution of [(AuCl)2dpppe] (0.20 g,
0.22 mmol) in CH2Cl2 (25 mL). The solution became yellow. After
five days InCl3 (0.10 g, 0.44 mmol) in THF (2 mL) was added to
the former solution, to produce colourless cubic crystals of 4 (see
Table 1). Yield 65% (0.16 g). C58H60Au4Cl6In2P4Se2 (2269.2): calcd.
C 30.70, H 2.67; found C 29.56, H 2.48.
Preparation of [Au4(TeGaCl3)2(dpph)2] (5): Te(SiMe3)2 (0.05 mL,
0.21 mmol) was added to a solution of [(AuCl)2dpph] (0.19 g,
0.21 mmol) in CH2Cl2 (25 mL). A solution of GaCl3 (0.04 g,
0.22 mmol) in THF (2 mL) was then added to the resultant dark
brown mixture After a few days colourless crystals of 5 had formed
(see Table 1). Yield 40% (0.10 g). C60H64Au4Cl6Ga2P4Te2 (2304.3):
calcd. C 31.27, H 2.80; found C 30.48, H 2.75.
Experimental Section
Preparation of [Au8Se4In(dppe)4](InCl4)3 (6): A solution of InCl3
(0.03 g, 0.12 mmol) in THF (2 mL) was added to a suspension of
[(AuCl)2dppe] (0.10 g, 0.12 mmol) in CH2Cl2 (25 mL). Se(SiMe3)2
(0.03 mL, 0.12 mmol) was added. The mixture was stirred for 2
hours. After 2 days colourless needles of 6 started to grow in the
flask (see Table 1). Complete crystallization was achieved by reduc-
ing the volume in vacuo. Yield 85% (0.09 g). C104H96Au8-
Cl12In4P8Se4 (4370.0): calcd. C 28.58, H 2.21; found C 28.15, H
2.21.
All experiments with chalcogenide ligands were carried out under
a dry nitrogen atmosphere. THF was dried over sodium-benzo-
phenone, and CH2Cl2 over P2O5 followed by distillation of the sol-
vents under nitrogen. Anhydrous InCl3 was obtained from Aldrich.
Preparation of [Ph3PAuCl]: A solution of [Au(thiodiglycol)Cl][30]
(0.51 g Au, 2.59 mmol) in MeOH (5 mL) was added to a solution
of PPh3 (0.68 g, 2.59 mmol) in CH2Cl2 (20 mL). The mixture was
stirred for 2 hours. The volume was reduced to a few milliliters and
water (50 mL) was added to produce a white solid. The solid was
filtered off, washed with water and dried in vacuo. Yield 85%
(1.09 g).
X-ray Analyses: STOE-IPDS II (Mo-Kα); data collection and re-
finement (SHELXTL-97).[31] CCDC-214542 to -214547 (for 1؊6)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.uk/
Preparation of [(AuCl)2(phosphane)]:[23,26] A solution of [Au(thiodi-
glycol)Cl][30] (0.40 g Au, 2.04 mmol) in MeOH (5 mL) was added conts/retrieving.html [or from the Cambridge Crystallographic
to a solution of phosphane (phosphane ϭ dppe, dpppe, dppph;
Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax:
1.02 mmol) in CH2Cl2 (10 mL). The final mixture was stirred for
(internat.) ϩ 44-1223-336-033; E-mail: deposit@ccdc.cam.ac.uk].
1104
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Eur. J. Inorg. Chem. 2004, 1100Ϫ1106

New Binary and Ternary Cluster Complexes
FULL PAPER
Table 1. Crystallographic data for compounds 1Ϫ6
1·2CH2Cl2
2·CH2Cl2·C5H12
3
4
5
6·CH2Cl2
Formula
C148H128Au10-
Cl10P8Se4
P1
C204H192Au12- C116H120Au10- C29H30Au2 -
C60H64Au4-
Cl6Ga2P4Te2
P21/c
C105H98Au8-
Cl16In4P8Se4
C2/c
Cl4P12Se4
P21/c
Cl5InP8Se4
C2/c
4
Cl3InP2Se
P1
2
¯
¯
Space group
Z
2
4
2
4
Temperature (K)
a (pm)
b (pm)
203(2)
203(2)
150(2)
190(2)
180(2)
180(2)
1750.4(4)
2014.7(4)
2027.5(4)
89.99(3)
89.98(3)
86.57(3)
7140(1)
2.231
1446.8(3)
1475.9(3)
2322.9(5)
90
94.76(3)
90
4943.1(17)
1.961
1.97 to 28.29
1870.3(4)
2169.5(4)
3112.5(6)
90
97.87(3)
90
12510(4)
2.304
1.53 to 27.16
1020.4(2)
1224.9(2)
1350.5(3)
73.29(3)
84.94(3)
78.19(3)
1581.7(5)
2.380
1298.7(3)
1463.6(3)
1856.9(4)
90
105.39(3)
90
3403.2(12)
2.249
1.63 to 24.92
3660.2(7)
1102.8(2)
3733.0(8)
90
116.01(3)
90
13542(5)
2.185
1.24 to 23.97
c (pm)
α (°)
β (°)
γ (°)
Volume (106 pm3)
Density (calcd.) (g/cm3)
Theta range for data
collection 2θmax (°)
Refl. collected
Ind. reflections
Rint
1.54 to 28.33
3.63 to 31.69
53765
32153
0.0979
14113
981
0.0595
0.1750
1.040
30257
12146
0.1409
10698
490
0.0848
0.2172
1.042
15551
9086
0.1085
5226
11852
6823
0.0519
6627
16894
5895
0.0635
4993
26799
10370
0.0621
8336
Refl. with Fo Ͼ 4σ(Fo)
Refined parameters
R1
wR2
Goodness of fit
650
343
352
473
0.0755
0.1806
1.026
0.0495
0.1456
1.298
0.0305
0.0791
0.655
0.0841
0.1939
1.230
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1106
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Eur. J. Inorg. Chem. 2004, 1100Ϫ1106