Russian Journal of Coordination Chemistry, Vol. 29, No. 12, 2003, pp. 838–844. Translated from Koordinatsionnaya Khimiya, Vol. 29, No. 12, 2003, pp. 902–908.
Original Russian Text Copyright © 2003 by Sharutin, Egorova, Sharutina, Ivanenko, Adonin, Starichenko, Pushilin, Gerasimenko.
Tetranuclear Bismuth Complex
6
Bi4(O)2(O2CC6H2F3-3,4,5,)8 · 2h -C6H5Me:
Synthesis and Structure
V. V. Sharutin*, I. V. Egorova*, O. K. Sharutina*, T. K. Ivanenko*, N. Yu. Adonin**,
V. F. Starichenko**, M. A. Pushilin***, and A. V. Gerasimenko***
*Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
**Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk, 630090 Russia
***Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 109, Vladivostok, 690022 Russia
Received December 9, 2002
Abstract—Tetranuclear organobismuth complex Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2η6-ë6ç5Me with four bis-
muth atoms joined via the bridging carboxylate ligands and oxygen atoms was studied using X-ray diffraction
analysis. The coordination sphere of either of the two terminal bismuth atoms contains the chelate carboxylate
ligand and the toluene molecule. For the bridging tricoordinated oxygen atoms, the Bi–O distances are
2.083(2), 2.119(2), and 2.276(2) Å. The average distance between the bismuth atom and the center of toluene
molecule is equal to 3.131 Å.
A number of bismuth complexes containing η6- ferent structural functions: six of them act as the bridg-
arene molecules were reported in [1–9]; however, only ing ligands, while the remaining two ligands behave as
one polynuclear bismuth compound of this type with chelate ligands.
bridging oxygen-containing ligand was described in
The central Bi atom is linked to one terminal Bi
[2], namely, the hexanuclear organobismuth complex.
atom through two bridging carboxylate ligands and the
In this compound, the coordination sphere of the bis-
bridging O atom and is bonded to another ligand
muth atoms contains, in addition to the η6-toluene and
through the bridging carboxylate ligand and the bridg-
ing O atom (Fig. 2). The µ3-bridging O atom is joined
η1-tetrahydrofurane, the bridging oxygen atoms and
pentafluorophenolate ligands (two terminal and ten
with two central and one terminal Bi atoms, thus clos-
bridging) [2]. The Bi···C6H5Me distance (3.073 Å) is
ing
centrosymmetrical
four-membered
noticeably shorter that the sum of the van der Waals
radii of bismuth and oxygen.
Bi(1)O(1)Bi(1)'O(1)' ring. The Bi(1)–O(1) and Bi(1)–
O(1)' distances in this ring are equal to 2.119(2) and
2.276(2) Å, respectively; the Bi(2)–O(1) bond length is
equal to 2.083(2) Å (the sum of the covalent radii of the
Bi and O atoms is equal to 2.31 Å [10]).
In this work, the synthesis and X-ray diffraction
analysis of tetranuclear organobismuth complex
Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2η6-ë6ç5Me (I) are
described.
All the three bridging carboxylate ligands are asym-
metrically coordinated to the Bi atoms, the coordina-
tion asymmetry being different. The Bi(1)–O(7) and
Bi(2)–O(6), Bi(1)–O(9) and Bi(2)–O(8) distances are
equal to 2.387(3) and 2.413(3), 2.384(3) and 2.241(3) Å,
respectively. The difference between the two bonds of
these ligands (∆) is equal to 0.026 and 0.143 Å, respec-
tively. The Bi(1)–O(4) and Bi(2)'–O(5) distances are
equal to 2.308(3) and 2.595(3) Å (∆ = 0.287 Å), i.e. the
coordination asymmetry of the Bi atoms in this carbox-
ylate ligand is most pronounced.
RESULTS AND DISCUSSION
Complex I was synthesized by reacting triphenyl-
bismuth with 3,4,5-trifluorobenzoic acid (at a molar
ratio of 1 : 2) in the presence of air oxygen:
4Ph3Bi + 8C6H2F3-3,4,5(é)ëéç + é2
toluene
Bi4(O)2[OC(O)C6H2F3-3,4,5]8 · 2C6H5Me.
It was established that triphenylbismuth is com-
pletely dephenylated under these conditions.
The coordination sphere of each terminal bismuth
According to X-ray diffraction data, centrosymmet- atom contains one chelate carboxylate ligand. The
rical tetranuclear complex I contains two pairs of struc- Bi(2)–O(2) and Bi(2)–O(3) distances are equal to
turally nonequivalent Bi atoms: two central (Bi(1) and 2.349(3) and 2.616(3) Å, respectively. Evidently, the
Bi(1)') and two terminal (Bi(2) and Bi(2)') (Fig. 1). The longer distances Bi(2)–O(3), Bi(2)'–O(3)' (2.616(3) Å)
bidentate 3,4,5-trifluorobenzoate ligands perform dif- and Bi(2)–O(5)', Bi(2)'–O(5) (2.595(3) Å) are due to
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