Russian Journal of Coordination Chemistry, Vol. 29, No. 5, 2003, pp. 317–321. Translated from Koordinatsionnaya Khimiya, Vol. 29, No. 5, 2003, pp. 341–345.
Original Russian Text Copyright © 2003 by Sharutin, Egorova, Ivanenko, Sharutina, Pavlushkina, Gerasimenko.
Tetraphenylbismuth 2,4-Dimethylbenzenesulfonate:
Synthesis and Structure
V. V. Sharutin, I. V. Egorova, T. K. Ivanenko, O. K. Sharutina,
I. I. Pavlushkina, and A. V. Gerasimenko
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 109, Vladivostok, 690022 Russia
Received October 1, 2001
Abstract—Tetraphenylbismuth 2,4-dimethylbenzenesulfonate was synthesized by reacting pentaphenylbismuth or
bromine with diphenylbismuth 2,4-dimethylbenzenesulfonate and its structure was established using X-ray diffrac-
tion analysis. The Bi atom has a distorted trigonal bipyramidal coordination. The Bi–C bond lengths are equal to
2.199(4)–2.227(4) Å; the Bi–O distance and axial CBiO angle are equal to 2.665(3) Å and 174.2(1)°, respectively.
Pentaphenylbismuth is known to phenylate bismuth The last reaction can be used for obtaining tetraphenyl-
derivatives with the general formula Ph3BiX2 to give bismuth arenesulfonates from diarylbismuth deriva-
Ph4BiX compounds (X = OSO2Ar) [1, 2]. To continue tives without their arylation with lithium compounds.
our studies of phenylating effect of Ph5Bi, we investi-
Earlier, we have reported the structure of compound
gated the reaction of this compound with diphenylbis-
II [1]. In this work, this structure was refined using X-
muth(III) arenesulfonates.
ray diffraction analysis. As in I [3], bismuth in structure
II has a distorted trigonal bipyramidal coordination
(see figure).
RESULTS AND DISCUSSION
The O(1) atom of 2,4-dimethylbenzenesulfonate
The reactions of pentaphenylbismuth with diphen-
group is located opposite to the phenyl substituent
ylbismuth arenesulfonates result in the redistribution of
C(41)–C(46) (the O(1)BiC(41) angle is equal to
radicals between Bi(V) and Bi(III) atoms and in the for-
174.2(1)°) and is at a distance of 2.654(3) Å from the
mation
of
tetraphenylbismuth
arenesulfonate
bismuth atom. The lengths of the Bi–C bonds of the
equatorial phenyl substituents C(11)–C(16), C(21)–
C(26), and C(31)–C(36) are close (2.202(4), 2.199(4),
and 2.201(4) Å). The angles between the axial Bi–
C(41) bond and the equatorial Bi–C bonds lie within
the 98.4(1)°–101.3(1)° range, while the bond angles
between the equatorial Bi–C bonds are equal to
112.6(1)°, 115.7(1)°, and 122.6(1)°. The bismuth atom
in II extends from the C(11)C(21)C(31) plane by
0.384 Å, which is comparable with the relevant value
for tetraphenylbismuth tosylate (0.41 Å) [3] and sug-
gests almost similar distortions of the trigonal bipyra-
midal coordination of the central atom in these com-
pounds.
Note that tetraphenylbismuth 2,5-dimethylbenzene-
sulfonate (III), which differs from II only in the posi-
tion of one of the methyl substituents in the benzene
ring of the arenesulfonate ligand [1, 2] has the ionic
structure as tetraphenylbismuth perchlorate [4]. Differ-
ent configurations of the bismuth atoms in isomers II
and III can be explained by different orientation (con-
sistent or inconsistent) of activating substituents in the
aromatic ring of the arenesulfonate ligand [1, 2]. If this
hypothesis is true, then one can expect that, for exam-
ple, tetraphenylbismuth 3,4-dimethylbenzenesulfonate,
in which the benzene ring of arenesulfonate ligand
(Ph4BiOSO2Ar, where Ar is C6H4Me-4 (I) or C6H3Me2-
2,4 (II)) and triphenylbismuth:
Ph5Bi + Ph2BiOSO2Ar
Ph4BiOSO2Ar + Ph3Bi.
These reactions proceed in ether solutions at 20°ë for
12 h. In this case, the purple color of Ph5Bi solutions
disappears, and crystals of tetraphenylbismuth arene-
sulfonate form. IR spectra and melting points of I and
II coincided with the corresponding parameters of the
compounds synthesized from pentaphenylbismuth and
arenesulfonic acid (acetone, 20°ë, 15 min) [1, 2].
We also synthesized tetraphenylbismuth arene-
sulfonates from diphenylbismuth arenesulfonate and
bromine in ether at 25°ë. One can suggest that the syn-
thesis of the target product proceeds through the forma-
tion of dibromophenylbismuth arenesulfonate as an
intermediate, which undergoes dispropotionation under
the synthesis conditions:
3Ph2BiOSO2C6H3Me2-2,4 + 3Br2
3[Ph2Bi(OSO2C6H3Me2-2,4)Br2]
Ph4BiOSO2C6H3Me2-2,4 + 2BiBr3
(II)
+ 2PhOSO2C6H3Me2-2,4.
1070-3284/03/2905-0317$25.00 © 2003 åÄIä “Nauka /Interperiodica”
Sharutin
