First molecular octahedral rhenium cluster complexes with terminal As- and Sb-donor ligands

Article abstract of DOI:10.1007/s11172-008-0213-6

Six new molecular octahedral cluster complexes with the general formulas trans-[{Re₆(μ₃-Q)₈}(EPh₃) ₄Br₂] and fac-[{Re₆(μ₃-Q) ₇(μ₃-Br)}(AsPh₃)₃Br₃] (Q = S or Se and E = As or Sb) were synthesized by the reactions of the cesium salts of the [{Re₆(μ₃-S)₈}Br ₆]^4-, [{Re₆(μ₃-Se) ₈Br₆]^3-, and [{Re₆(μ₃- Q)₇(μ₃-Br)}Br₆]^3- anions with molten triphenylarsine (AsPh₃) and triphenylantimony (SbPh ₃), respectively. The compositions and structures of the resulting complexes were established by single-crystal X-ray diffraction and confirmed by elemental analysis and vibrational spectroscopy. The compositions and structures of the complexes depend on the composition of the cluster core in the starting salts. The luminescence spectra were recorded for powdered samples of all these compounds and the earlier described complexes trans-[{Re₆Q ₈}(PPh₃)₄Br₂] and fac-[{Re ₆Q₇Br}(PPh₃)₃Br₃].

Full text of DOI:10.1007/s11172-008-0213-6

Russian Chemical Bulletin, International Edition, Vol. 57, No. 8, pp. 1644—1649, August, 2008
1644
First molecular octahedral rhenium cluster complexes
with terminal Asꢀ and Sbꢀdonor ligands
M. A. Shestopalov, Yu. V. Mironov, K. A. Brylev, and V. E. Fedorov
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences,
3 prosp. Akad. Lavrentieva, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383) 330 9489. Eꢀmail: yuri@che.nsk.su
Six new molecular octahedral cluster complexes with the general formulas transꢀ
[{Re6(µ ꢀQ)8}(EPh3)4Br2] and facꢀ[{Re6(µ ꢀQ)7(µ ꢀBr)}(AsPh3)3Br3] (Q = S or Se and
3
3
3
E = As or Sb) were synthesized by the reactions of the cesium salts of the [{Re6(µ ꢀS)8}Br6]4–
,
[{Re6(µ ꢀSe)8}Br6]3–, and [{Re6(µ ꢀQ)7(µ ꢀBr)}Br6]3– anions with molten tri3phenylarsine
3
(AsPh3) and triphenylantimony (Sb3Ph3), re3spectively. The compositions and structures of the
resulting complexes were established by singleꢀcrystal Xꢀray diffraction and confirmed by
elemental analysis and vibrational spectroscopy. The compositions and structures of the comꢀ
plexes depend on the composition of the cluster core in the starting salts. The luminescence
spectra were recorded for powdered samples of all these compounds and the earlier described
complexes transꢀ[{Re6Q8}(PPh3)4Br2] and facꢀ[{Re6Q7Br}(PPh3)3Br3].
Key words: rhenium, octahedral chalcogenide clusters, triphenylarsine, triphenylantimony,
crystal structure.
Results and Discussion
Octahedral rhenium cluster complexes with the
general formula [Re6Q8L6] (Q = S, Se, or Te; L are inorꢀ
ganic or organic ligands) have been extensively studied in
recent years. This class of compounds has attracted great
attention because these compounds exhibit interesting
properties, in particular, the redox, luminescence, and
magnetic properties. Hybrid metal clusters with organic
ligands are of particular interest. Rhenium cluster comꢀ
plexes with organic Nꢀ and Pꢀdonor ligands are the most
typical representatives of this class of compounds.1,2 For
many years, the main approach to the synthesis of such
complexes has been based on the replacement of terminal
ligands in solutions. In most cases, the oxidized anionic
complexes [Re6Q8Y6]3– (Q = S or Se; Y = Cl, Br, or I),
which are characterized by higher reactivity compared to
the unoxidized complexes, were used as the starting comꢀ
pounds.1—9 Recently, we have shown that the reactions
of molten organic ligands are equally efficient for the
replacement of terminal ligands in both oxidized and
unoxidized chalcogenide cluster complexes. We have used
this method to synthesize complexes with 3,5ꢀdimethylꢀ
pyrazole (3,5ꢀMe2pzH)10,11 and triphenylphosphine (PPh3).12
As a continuation of our investigations, in the present
study we performed the reactions of cesium salts of the
Six new molecular octahedral rhenium cluster comꢀ
plexes, transꢀ[{Re6S8}(AsPh3)4Br2] (1), transꢀ[{Re6Se8}ꢀ
(AsPh3)4Br2] (2), transꢀ[{Re6S8}(SbPh3)4Br2] (3), transꢀ
[{Re6Se8}(SbPh3)4Br2] (4), facꢀ[{Re6S7Br}(AsPh3)3Br3]
(5), and facꢀ[{Re6Se7Br}(AsPh3)3Br3] (6), were synthesized.
The cesium salts of the anionic chalcobromide complexes
Cs4[Re6S8Br6]•2H2O,13 Cs3[Re6Se8Br6]•2H2O,14 and
Cs3[Re6Q7Br7]•H2O (Q = S or Se)15 were used as the starting
reagents. The reactions were carried out with an excess of
the corresponding ligand. The reaction mixtures were kept
in sealed tubes at 200 °C for two days. To obtain single
crystals, the furnace was slowly cooled to room temperaꢀ
ture at a rate of 10 deg h–1. Crystals suitable for Xꢀray
diffraction were selected directly from the solidified melts.
In all cases, we prepared octahedral rhenium cluster
complexes, in which the Re6 octahedron is located inside
the Q8 cube (compounds 1—4) or the Q7Br cube (comꢀ
pounds 5 and 6), where Q = S or Se.
The Re—Re and Re—Q distances in isostructural comꢀ
pounds 1—4 are typical of octahedral rhenium chalcoꢀ
genide cluster complexes. Four Re atoms of the cluster
core {Re6Q8} in the equatorial plane are coordinated by
EPh3 molecules. The other two Re atoms are coordinated
by bromine atoms to form molecular complexes with the
general formula transꢀ[{Re6(µ3ꢀQ)8}(EPh3)4Br2] (Fig. 1).
Selected interatomic distances in the structures of 1—4
are given in Table 1.
anionic cluster complexes [{Re6S8}Br6]4–, [{Re6Se8}Br6]3–
,
and [{Re6Q7Br}Br6]3– (Q = S or Se) with molten triphenylꢀ
arsine and triphenylantimony and obtained a representaꢀ
tive series of molecular complexes containing the cluster
cores {Re6Q8}2+ and {Re6Q7Br}3+
.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1614—1619, August, 2008.
1066ꢀ5285/08/5708ꢀ1644 © 2008 Springer Science+Business Media, Inc.

Re6 Cluster complexes with AsPh3 and SbPh3
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1645
C
As
Br
Re
S
C
As
Br
Re
S
Fig. 1. Structures of molecular complexes 1—4 exemplified by
transꢀ[{Re6S8}(AsPh3)4Br2] (1) (hydrogen atoms are omitted).
Fig. 2. Structures of molecular complexes 5 and 6 exemplified by
facꢀ[{Re6S7Br}(AsPh3)4Br3] (5) (hydrogen atoms are omitted).
The crystal structures of isostructural compounds
5 and 6 consist of the molecular cluster complexes
facꢀ[{Re6(µ3ꢀQ)7(µ3ꢀBr)}(AsPh3)3Br3]. The cluster core
{Re6(µ3ꢀQ)7(µ3ꢀBr)} is composed of the Re6 octahedron
located inside the Q7Br pseudocube, in which the µ3ꢀBr
ligand is coordinated to three rhenium atoms bound to
three terminal Br ligands. The other three rhenium atoms
are coordinated by AsPh3 molecules. The structure of the
complexes facꢀ[{Re6(µ3ꢀQ)7(µ3ꢀBr)}(AsPh3)3Br3] in comꢀ
pounds 5 and 6 is presented in Fig. 2.
In compound 5, the Re—Re distances between the
three rhenium atoms coordinated by the µ3ꢀbromine
atom (2.6207(5)—2.6297(5) Å) are longer than the Re—Re
distances between the rhenium atoms coordinated by the
µ3ꢀS atoms (2.5808(5)—2.6077(5) Å). This fact is
accounted for by the difference in the atomic radii of S
and Br (the matrix effect). There are no such differences
in the interatomic distances in the cluster core of comꢀ
pound 6, because the bromine and selenium atoms have
similar radii (see Table 1).
Table 1. Selected interatomic distances (d)
Complex
d/Å
Re—Re
Re—(µ ꢀQ)
Re—(µ ꢀBr)
Re—E
Re—Brterminal
2.5466(4)
3
3
1
2.5963(2)—
2.6065(2)
2.6257(6)—
2.6394(6)
2.5828(6)—
2.5979(6)
2.5938(7)—
2.6161(6)
2.5808(5)—
2.6297(5)
2.6117(5)—
2.6485(4)
2.5884(3)—
2.5972(3)
2.6284(4)—
2.6542(4)
2.3964(9)—
2.4151(10)
2.5092(12)—
2.5297(11)
2.382(3)—
2.422(3)
2.4850(16)—
2.5203(12)
2.376(2)—
2.433(2)
2.4900(9)—
2.5317(8)
2.3807(16)—
2.4128(15)
2.5013(7)—
2.5267(7)
—
—
—
—
2.5466(4)—
2.5876(4)
2.5906(13)—
2.5936(12)
2.7319(8)—
2.7345(9)
2.7030(9)—
2.7054(9)
2.5679(10)—
2.5883(10)
2.5748(9)—
2.5926(9)
2.517(2)—
2.522(2)
2
2.5651(12)
2.5419(12)
2.5449(13)
3
4
5
2.6095(10)—
2.6187(10)
2.6133(9)—
2.6195(9)
—
2.5151(10)—
2.5391(11)
2.5352(10)—
2.5602(10)
2.5471(7)
6
[Re6S8(PPh3)4Br2]12
[Re6Se8(PPh3)4Br2]12
[Re6S7Br(PPh3)3Br3]12
[Re6Se7Br(PPh3)3Br3]12
—
2.515(2)—
2.522(2)
2.5672(7)
2.5822(5)—
2.6268(5)
2.6130(6)—
2.6578(7)
2.381(2)—
2.469(2)
2.4864(10)—
2.5303(11)
2.5874(11)—
2.5970(11)
2.6107(11)—
2.6184(11)
2.498(2)—
2.515(1)
2.504(3)—
2.539(2)
2.5190(10)—
2.5443(10)
2.5374(13)—
2.5643(12)

1646
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
Shestopalov et al.
Numerous examples of octahedral chalcogenide clusꢀ
ter complexes of rhenium and other transition metals (Cr,
Fe, Co, Mo, Ru, and W) with terminal Pꢀdonor ligands,
in particular, with PPh3 and PEt3, have been described in
the literature.3,4,12,16—27 However, only one structure of an
octahedral transition metal cluster complex with terminal
Asꢀdonor ligands was found in the Cambridge Structural
Database. This is the structure of the compound containꢀ
ing a zirconium complex with trimethylarsine with the
formula transꢀ[{Zr6(µ3ꢀH)4(µ2ꢀCl)12}(AsMe3)4Cl2]•CH2Cl2.28
In addition, the structure of the octahedral rhenium
cluster complex [{Re6S6As2}(PPr3)6]•CH3CN containing
an As atom as the µ3ꢀbridging ligand and the tripropylꢀ
phosphine (PPr3) molecules as the terminal ligands was
documented.29 No other examples of octahedral transiꢀ
tion metal cluster complexes, in which the metal atom of
the cluster core is bound to the arsenic atom, were found
in the literature. Examples of M6 clusters with Sbꢀdonor
ligands are also lacking.
to the rhenium atoms, which are bound exclusively to the
µ3ꢀQ atoms, as demonstrated earlier for the isostructural
complexes facꢀ[{Re6Q7Br}(PPh3)3Br3].12
The luminescence spectra were recorded for powdered
samples of compounds 1—6, as well as for the
I/(rel. units)
1
5000
4000
3000
2000
1000
0
2
3
500
600
700
800
λ/nm
The compounds described in the present study extend
the range of the already known complexes with the general
formulas transꢀ[{Re6Q8}(PPh3)4Br2] and facꢀ[{Re6Q7Br}ꢀ
(PPh3)3Br3] (Q = S or Se).12 Compounds 1—4 are isoꢀ
structural with transꢀ[{Re6Q8}(PPh3)4Br2]; compounds 5
and 6, with facꢀ[{Re6Q7Br}(PPh3)3Br3]. Selected interꢀ
atomic distances in the clusters under consideration and
in related hexarhenium triphenylphosphine cluster comꢀ
plexes are given in Table 1. The Re—E (E = P, As, or Sb)
and Re—Q (Q = S or Se) distances in the octahedral
clusters increase in the series P < As < Sb and S < Se,
respectively, which is attributed to an increase in the
atomic radius in the series P < As < Sb and S < Se,
respectively.
The distinguishing feature of compounds 5 and 6
is that the bromine atom in the cluster core {Re6Q7Br} is
ordered. Earlier, only a few octahedral rhenium cluster
complexes with ordered µ3ꢀligands in mixedꢀligand chalcoꢀ
genide cluster cores with the formulas facꢀ[{Re6Q7Br}ꢀ
(PPh3)3Br3], cisꢀ[{Re6S6Br2}(PPh3)2Br4], transꢀ[{Re6S6Br2ꢀ
(PPh3)2}Br4],12 and cisꢀ[{Re6Te6Cl2}(TeCl2)2Cl4] (see Ref. 30)
have been described. However, the µ3ꢀcoordinated atoms
in the majority of the known Re6 complexes with heteroꢀ
ligand cluster cores are disordered over eight sites. In the
structures of 5 and 6, the Br atom occupies the only site in
the vicinity of three rhenium atoms bound to the terminal
Br atoms. All known octahedral rhenium cluster compꢀ
lexes with the ordered arrangement of the internal acido
ligands are characterized by the following feature: the
neutral terminal ligands are coordinated to the rhenium
atoms, which are bound exclusively to the µ3ꢀQ atoms
(Q = S, Se, or Te) to form molecular (neutral) comꢀ
plexes. Presumably, the specific electron density distribuꢀ
tion at the rhenium atoms in the starting complexes
[Re6Q7Br7]3– (Q = S or Se) is one of the factors responꢀ
sible for the coordination of the neutral terminal ligands
Fig. 3. Luminescence spectra of transꢀ[{Re6S8}(PPh3)4Br2] (1)
and compounds 1 (2) and 3 (3).
I/(rel. units)
8000
7000
6000
5000
4000
3000
2000
1000
0
2
1
3
500
600
700
800
λ/nm
Fig. 4. Luminescence spectra of transꢀ[{Re6S8}(PPh3)4Br2] (1)
and compounds 2 (2) and 4 (3).
I/(rel. units)
5000
4000
3000
2000
1
2
1000
0
500
600
700
800
900 λ/nm
Fig. 5. Luminescence spectra of facꢀ[{Re6Se7Br}(PPh3)3Br3] (1)
and compound 6 (2).

Re6 Cluster complexes with AsPh3 and SbPh3
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1647
I/(rel. units)
Table 2. Luminescence properties of compounds 1—6, transꢀ
[{Re6Q8}(PPh3)4Br2], and facꢀ[{Re6Q7Br}(PPh3)3Br3] (Q = S or Se)
10000
Compound
λ/nm
1
8000
transꢀ[{Re6S8}(PPh3)4Br2]
765
780
750
765
745
750
770
775
770
770
transꢀ[{Re6Se8}(PPh3)4Br2]
transꢀ[{Re6S8}(AsPh3)4Br2] (1)
transꢀ[{Re6Se8}(AsPh3)4Br2] (2)
transꢀ[{Re6S8}(SbPh3)4Br2] (3)
transꢀ[{Re6Se8}(SbPh3)4Br2] (4)
facꢀ[{Re6S7Br}(PPh3)3Br3]
6000
4000
2
2000
0
facꢀ[{Re6Se7Br}(PPh3)3Br3]
facꢀ[{Re6S7Br}(AsPh3)3Br3] (5)
facꢀ[{Re6Se7Br}(AsPh3)3Br3] (6)
500
600
700
800
λ/nm
cooled to room temperature at a rate of 10 °C h–1. The reaction
product was washed off from the excess organic ligand with
diethyl ether; CsBr, which was formed in the reaction, and the
unconsumed cluster complex were washed off with water. Single
crystals suitable for Xꢀray diffraction studies were taken from
the solidified melts.
Fig. 6. Luminescence spectra of compound 5 (1) and facꢀ
[{Re6S7Br}(PPh3)3Br3] (2).
earlier described complexes transꢀ[{Re6Q8}(PPh3)4Br2]
and facꢀ[{Re6Q7Br}(PPh3)3Br3]12 (Figs 3—6). In all
spectra, the emission maxima for the seleniumꢀcontainꢀ
ing clusters slightly shift to longer wavelengths relative to
those of their sulfurꢀcontaining analogs and depend also
on the nature of the donor atoms of the terminal ligands
(Table 2). The wavelength corresponding to the luminesꢀ
cence maximum depends on the nature of terminal ligands
and increases in the series SbPh3 < AsPh3 < PPh3. This
dependence is clearly seen in Figs 3 and 5 by exemples
of the complexes transꢀ[{Re6S8}(EPh3)4Br2] (E = P, As,
or Sb) and facꢀ[{Re6Se7Br}(EPh3)3Br3] (E = P or As).
Earlier, it has been noted12 that the facꢀ[{Re6S7Br}ꢀ
(PPh3)3Br3] compound does not exhibit luminescence in
solution. It appeared that this compound, like the AsPh3ꢀ
containing analog (5), is almost nonꢀemissive in the solid
state as well (Fig. 6).
transꢀOctakis(µ ꢀsulfido)tetrakis(triphenylarsino)dibromoꢀ
3
hexarhenate (Re—Re), transꢀ[{Re6S8}(AsPh3)4Br2] (1). The
yield was 54 mg (47.4%). Found (%): C, 31.04; H, 2.32; S, 9.27.
C72H60Br2As4Re6S8. Calculated (%): C, 31.35; H, 2.19; S, 9.30.
According to EDAX data, the element ratio in the sample
Re : S : Br : As = 6 : 7.7 : 2.1 : 4.2. IR (KBr), ν/cm–1: 416 (Re—S).
transꢀOctakis(µ ꢀselenido)tetrakis(triphenylarsino)dibromoꢀ
3
hexarhenate (Re—Re), transꢀ[{Re6Se8}(AsPh3)4Br2] (2). The
yield was 113 mg (95.5%). Found (%): C, 27.64; H, 1.86.
C72H60Br2As4Re6Se8. Calculated (%): C, 27.60; H, 1.93.
According to EDAX data, the element ratio in the sample
Re : Se : Br : As = 6 : 8.1 : 2 : 3.9.
transꢀOctakis(µ ꢀsulfido)tetrakis(triphenylantimony)dibromoꢀ
3
hexarhenate (Re—Re), transꢀ[{Re6S8}(SbPh3)4Br2] (3). The
yield was 60 mg (43.3%). Found (%): C, 29.41; H 2.00; S, 8.70.
C72H60Br2Sb4Re6S8. Calculated (%): C, 29.36; H, 2.05; S, 8.71.
According to EDAX data, the element ratio in the sample
Re : S : Br : Sb = 6 : 7.8 : 2.3 : 3.7. IR (KBr), ν/cm–1: 415 (Re—S).
transꢀOctakis(µ ꢀselenido)tetrakis(triphenylantimony)dibromoꢀ
hexarhenate (Re—3Re), transꢀ[{Re6Se8}(SbPh3)4Br2] (4). The
yield was 93 mg (74.2%). Found (%): C, 25.99; H, 1.91.
C72H60Br2Sb4Re6Se8. Calculated (%): C, 26.04; H, 1.82.
According to EDAX data, the element ratio in the sample
Re : Se : Br : Sb = 6 : 8.2 : 1.8 : 3.8.
Experimental
The starting salts Cs4[Re6S8Br6]•2H2O, Cs3[Re6Se8Br6]•2H2O,
and Cs3[Re6Q7Br7]•H2O (Q = S or Se) were synthesized by the
highꢀtemperature ampoule method according to procedures
described earlier.13—15
The elemental analysis was carried out on a Carlo Erba 1106
instrument. The ratios of the heavy elements were determined
by energy dispersive Xꢀray analysis (EDAX) on a JSMꢀ6700F
scanning electron microscope. The IR spectra were recorded on
a Scimitar IFS2000 Fourierꢀtransform IR spectrometer. The IR
spectra of compounds 1—6 show all peaks assigned to vibrations
of the organic ligand. The luminescence spectra of powdered
samples were recorded at room temperature on a Hitachi
Fꢀ4500 spectrofluorimeter.
Synthesis of complexes 1—6. Cesium salts of the correspondꢀ
ing octahedral cluster complexes were heated with excess AsPh3
or SbPh3 (the salts of the cluster complexes and the ligands were
taken in amounts of 100 mg) in sealed glass tubes to 200 °C and
allowed to stand for two days. Then the reaction mixture was
facꢀHeptakis(µ ꢀsulfido)(µ ꢀbromido)tris(triphenylarsino)ꢀ
tribromohexarhenat3e (Re—Re), 3facꢀ[{Re6S7Br}(AsPh3)3Br3] (5).
The yield was 30 mg (27.8%). Found (%): C, 25.64; H, 1.72; S,
8.55. C54H45As3Br4Re6S7. Calculated (%) C, 25.14; H, 1.76; S,
8.70. According to EDAX data, the element ratio in the sample
Re : S : Br : As = 6 : 6.9 : 4.3 : 2.8. IR (KBr), ν/cm–1: 419 (Re—S).
facꢀHeptakis(µ ꢀselenido)(µ ꢀbromido)tris(triphenylarsino)ꢀ
3
tribromohexarhena3te (Re—Re), facꢀ[{Re6Se7Br}(AsPh3)3Br3]
(6). The yield was 100 mg (93.5%). Found (%): C, 22.22;
H, 1.53. C54H45As3Br4Re6Se7. Calculated: C, 22.30; H, 1.56.
According to EDAX data, the element ratio in the sample
Re : Se : Br : As = 6 : 7.1 : 3.8 : 2.9.
Xꢀray diffraction study. The Xꢀray diffraction data for the
structure determination were collected according to a standard

1648
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
Shestopalov et al.
Table 3. Crystallographic data for compounds 1—3
Parameter
1
2
3
Molecular formula
Molecular weight
Crystal dimensions/mm
Crystal system
Space group
a/Å
b/Å
c/Å
C72H60As4Br2Re6S8
2758.38
0.10×0.08×0.06
Monoclinic
P21/c
C72H60As4Br2Re6Se8
3133.58
C72H60Sb4Br2Re6S8
2945.70
0.80×0.10×0.10
Monoclinic
P21/c
12.5680(13)
17.9594(16)
18.4964(12)
0.12×0.10×0.06
Monoclinic
P21/c
12.4314(5)
16.4658(11)
19.6441(13)
12.4453(3)
16.4323(4)
19.3363(5)
α/deg
β/deg
γ/deg
100.716(1)
100.983(2)
95.970(4)
V/Å
3885.4(2)
2
2.358
12.282
3947.4(4)
2
2.636
15.566
4152.2(6)
2
2.356
11.184
Z
ρ
calc/g cm–3
µ/mm–1
2θ/deg
Transmission factors
0.526; 0.373
0.455; 0.257
0.401; 0.041
Number of measured/independent
reflections
Rint
Number of observed reflections
28192/9625
0.0250
7965
32597/9552
0.0729
5017
41481/10018
0.0623
5603
Number of refined parameters
415
415
343
R (I > 2σ(I))
R1
wR2
0.0222
0.0513
0.0510
0.1099
0.0497
0.1319
R (based on all reflections)
R1
wR2
0.0322
0.0536
0.1039
0.1243
0.0947
0.1414
Table 4. Crystallographic data for compounds 4—6
Parameter
4
5
6
Molecular formula
Molecular weight
C72H60Sb4Br2Re6Se8
3320.90
C54H45As3Br4Re6Se7
2579.92
C54H45As3Br4Re6Se7
2908.22
Crystal dimensions/mm
0.15×0.10×0.10
Monoclinic
P21/c
0.10×0.10×0.08
Triclinic
P –1
0.16×0.14×0.08
Triclinic
Crystal system
Space group
a/Å
b/Å
c/Å
α/deg
β/deg
γ/deg
P –1
12.543(2)
17.821(3)
18.772(3)
77.081(1)
96.749(7)
90
4166.8(13)
2
2.647
11.8167(5)
14.8575(7)
20.2311(9)
77.449(2)
76.129(2)
67.721(1)
3155.9(2)
2
11.8123(7)
15.0302(8)
20.4986(9)
75.319(2)
67.930(2)
3232.2(3)
2
2.988
19.162
V/Å
Z
ρ
calc/g cm–3
2.715
15.820
µ/mm–1
14.439
2θ/deg
Transmission factors
0.326; 0.221
0.364; 0.301
0.301; 0.150
Number of measured/independent
reflections
Rint
Number of observed reflections
26243/10232
0.0496
6595
38064/15092
0.0552
9096
28883/15282
0.0282
8446
Number of refined parameters
343
667
667
R (I > 2σ(I))
R1
wR2
0.0523,
0.1575
0.0478,
0.1125
0.0378,
0.0821
R (based on all reflections)
R1
wR2
0.0915,
0.1710
0.0910
0.1270
0.0848,
0.0919

Re6 Cluster complexes with AsPh3 and SbPh3
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1649
procedure on a singleꢀcrystal automated BrukerꢀNonius
X8APEX CCD diffractometer (MoKα radiation, λ = 0.71073 Å,
graphite monochromator) at room temperature. Semiempirical
absorption corrections were applied using the SADABS
program.31
The structures were solved by direct methods followed by
calculations of difference Fouier maps and the refinement of the
positional and anisotropic thermal parameters by the fullꢀmatrix
leastꢀsquares method with the use of the SHELXꢀ97 program
package.32 The hydrogen atoms in the AsPh3 and SbPh3
molecules were positioned geometrically. The Xꢀray diffraction
data collection and refinement statistics are given in Tables 3
and 4. The structural data for complexes 1—6 were deposited with
the Cambridge Structural Database (CCDC 646770—646775,
respectively) and can be obtained from the authors.
11. Y. V. Mironov, K. A. Brylev, M. A. Shestopalov, S. S.
Yarovoi, V. E. Fedorov, H. Spies, H.ꢀJ. Pietzsch, H. Stephan,
G. Geipel, G. Bernhard, W. Kraus, Inorg. Chim. Acta, 2006,
359, 1129.
12. M. A. Shestopalov, Y. V. Mironov, K. A. Brylev, S. G.
Kozlova, V. E. Fedorov, H. Spies, H.ꢀJ. Pietzsch, H.
Stephan, G. Geipel, G. Bernhard, J. Am. Chem. Soc., 2007,
129, 3714.
13. S. S. Yarovoi, S. F. Solodovnikov, Yu. V. Mironov, Zh.
Strukt. Khim., 2003, 44, 318 [Russ. J. Struct. Chem., 2003, 44
(Engl. Transl.)]
14. S. S. Yarovoi, Y. V. Mironov, D. Y. Naumov, Y. V. Gatilov,
S. G. Kozlova, S.ꢀJ. Kim, V. E. Fedorov, Eur. J. Inorg.
Chem., 2005, 3945.
15. S. S. Yarovoi, S. F. Solodovnikov, Y. V. Mironov, V. E.
Fedorov, Mater. Res. Bull., 1999, 34, 1345.
16. Z. Zheng, R. H. Holm, Inorg. Chem., 1997, 36, 5173.
17. H. D. Selby, P. Orto, M. D. Carducci, Z. Zheng, Inorg.
Chem., 2002, 41, 6175.
18. F. Cecconi, C.A. Ghilardi, S. Midollini, A. Orlandini, Polyꢀ
hedron, 1986, 5, 1986.
We thank D. Yu. Naumov (A. V. Nikolaev Institute of
Inorganic Chemistry of the Siberian Branch of the Rusꢀ
sian Academy of Sciences) for performing the Xꢀray difꢀ
fraction studies on an automated Bruker Nonius X8Apex
diffractometer.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos. 05ꢀ03ꢀ
32123, 05ꢀ03ꢀ32745, and 06ꢀ03ꢀ89503ꢀNNS).
19.
D. Fenske, J. Hachgenei, J. Ohmer, Angew. Chem., Int. Ed.,
1985, 24, 706.
20. D. Fenske, J. Ohmer, J. Hachgenei, Angew. Chem., Int. Ed.,
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21. S. Kamiguchi, H. Imoto, T. Saito, T. Chihara, Inorg. Chem.,
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22. F. Cecconi, C. A. Ghilardi, S. Midollini, A. Orlandini, P.
Zanello, J. Chem. Soc., Dalton Trans., 1987, 831.
23. Yu. V. Mironov, Zh. S. Kozhomuratova, D. Yu. Naumov,
V. E. Fedorov, Zh. Strukt. Khim., 2007, 48, 389 [Russ. J.
Struct. Chem., 2007, 48 (Engl. Transl.)]
24. T. Saito, N. Yamamoto, T. Yamagata, J. Am. Chem. Soc.,
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Received June 7, 2007