Tetraphenylbismuth 2,4-Dimethylbenzenesulfonate: Synthesis and Structure

Tetraphenylbismuth 2,4-dimethylbenzenesulfonate was synthesized by reacting pentaphenylbismuth or bromine with diphenylbismuth 2,4-dimethylbenzenesulfonate and its structure was established using X-ray diffraction 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.     

Triphenylbismuth Bis(2,4,6-Tribromophenoxide): Synthesis and Structure

A reaction of triphenylbismuth with 2,4,6-tribromophenol and hydrogen peroxide (molar ratio 1 : 2 : 1) in ether affords triphenylbismuth bis(2,4,6-tribromophenoxide). The complex obtained was structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Bi atom is a trigonal bipyramid with axial aroxy groups. The Bi–C and Bi–O bond lengths are 2.202(4), 2.203(4), 2.212(4) and 2.241(3), 2.245(3) Å, respectively. The intramolecular Bi···Br(1,4) contacts are 3.629(1) and 4.077(1) Å, respectively.     

New Method for Preparing Tetraphenylbismuth Arenesulfonate

Russian Journal of General Chemistry -     

Arylation of Aryl- and Diarylbismuth Arenesulfonates with Pentaarylantimony

Pentaarylantimony Ar₃Sb (Ar = Ph, p-Tol) arylates diarylbismuth arylsulfonates Ar₂BiOSO₂Ar' (Ar' = C₆H₄Me-4; C₆H₃Me₂-2,4, C₆H₃Me₂-2,5) in ether at 20°C (48 h) to form triarylbismuth in yields of up to 95%. The second reaction product is tetraarylantimony arenesulfonate. The reaction of pentaphenylantimony with phenylbismuth bis(arenesulfonate) PhBi(OSO₂Ar')₂ under the same conditions leads to formation of diphenylbismuth arenesulfonate and tetraphenylantimony arenesulfonate in yields of up to 90%.     

Synthesis,structure and reactions of μ-oxobis(arenesulfonatotriarylbismuth)

Hydrolysis of triarylbismuth bis(arenesulfonates) in acetone gives bismuth derivatives of the general formula [Ar₃Bi(OSO₂Ar)]₂O (Ar = Ph, p-Tol; Ar = Ph, C₆H₄Me-4, C₆H₃Me₂-2,4, C₆H₃Me₂-3,4). The structure of -oxobis[(3,4-dimethylbenzenesulfonato)triphenylbismuth] was established by means of X-ray diffraction. The molecule has a linear centrosymmetric structure with the bridging oxygen atom in the inversion center. The bismuth atom has a distorted trigonal bipyramidal coordination with the bridging oxygen atom and the arenesulfonate group in axial positions. The Bi-C and Bi-O_term distances are 2.200(2), 2.204(3), and 2.442(2) Å, and the Bi-O_br distances are 2.067(1) Å.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1466–1471.Original Russian Text Copyright © 2004 by Sharutin, Egorova, Sharutina, Ivanenko, Pavlushkina, Gerasimenko, Pushilin.This revised version was published online in April 2005 with a corrected cover date.     

Some features of EPR and optical spectra of vanadium in aluminophosphate glasses

The EPR and optical spectra of vanadium in glasses of ternary Al₂O₃P₂O₅SiO₂ and Al₂O₃P₂O₅B₂O₃ systems have been measured. The results were compared with earlier data for vanadium in binary phosphate, aluminophosphate and silicaphosphate glasses and with results of de-Biasi for V⁴⁺ in crystalline powder α-crystobalite AlPO₄. The superpositions of two hyperfine spectra (ASB-I and ASB-II) were found for many glasses of ternary systems. Both spectra can be attributed to VO²⁺ ions. The intensity ratio of the ASB-II spectrum to ASB-I depends on glass composition but is great (> 7) for all the glasses. Only the ASB-II spectrum was observed in glasses with low concentration of Al₂O₃. The spectral parameters of ASB-II spectrum are g_| = 1.916–1.921; g_⊥ 1.980–1.988; A_| = (188?190) × 10^?4cm^?1 and A_⊥ = (74–77) × 10^?4cm^?1. Three intense bands at 370, 455 and 700 ans 720 nm observed in these glasses can be attributed to V³⁺ ions. The excellent agreement of the parameters of the EPR spectrum of V⁴⁺ ions in crystalline α-crystobalite AIPO₄ and ASB-II spectra in the glasses under study suggest the identical electron structure of the paramagnetic species. This species is believed to be characterized by optical bands at 680 and 790 nm which have been observed by de Biasi. The orbital mixing coefficients indicate strong tetragonal distortion of vanadyl complexes responsible for the ASB-II spectrum. It is assumed that VO²⁺ ions responsible for this spectrum act as modifiers fitting into the relatively small holes of the three-dimensional networks of phosphate glasses containing no cations of large radii. The microscopic basicity of oxygens in such holes must be about 0.48.     

Reaction of Triphenylbismuth Bis(arenesulfonates) with Triphenylstibine

Tetraphenylantimony arenesulfonates and diphenylbismuth arenesulfonates were prepared by reaction of triphenylbismuth bis(arenesulfonates) with triphenylstibine in toluene at 25°C. The crystal and molecular structure of diphenylbismuth 2,4-dimethylbenzenesulfonate was studied by single crystal X-ray diffraction. The molecules of the compound in the crystal form chains of Ph₂BiOSO₂C₆H₃Me₂-2,4 fragments linked with oxygen atoms of the sulfo group of the bridging arenesulfonate ligand.     

μ-Oxo-Bis[(arenesulfonato)triphenylantimony]: Synthesis and Structure

-Oxo-bis[(4-methylbenzenesulfonato)triphenylantimony] (I) and -oxo-bis[(2,5-dimethylbenzenesulfonato)triphenylantimony] (II) were synthesized by reacting triphenylstibine Ph₃Sb with tri-p-tolylbismuth bis(4-methylbenzenesulfonate) and tri-p-tolylbismuth bis(2,5-dimethylbenzenesulfonate), respectively, in toluene in the presence of air moisture. According yo X-ray diffraction data, the antimony atoms in the compounds synthesized have a distorted trigonal bipyramidal configuration. The SbOSb angles are equal to 138.5(2)° and 180°, respectively. A bent molecule I contains the Sb(1)···Sb(2) (3.690(1) Å) and Sb···S(1,2) (3.521(2), 3.559(2) Å) intramolecular contacts. In a linear molecule II, the Sb···S distances are equal to 3.438(1) Å.