Phenyl Bismuth(V) Derivatives Ph3Bi[OC6H3(NO2)(2)-2,5](2) . 0.5PhH, Ph4BiOC6H3(NO2)(2)-2,5 and Ph4BiBr: Synthesis and Structure
Senchurin, VS; Sharutin, VV; Sharutina, O; ,
Triphenylbismuth, 2,5-dinitrophenol, and tert-butyl hydroperoxide (molar ratio, 1 : 2 : 1) react in diethyl ether to form triphenylbismuth bis(2,5-dinitrophenoxide) separated after recrystallization from benzene in the solvated form Ph3Bi[OC6H3(NO2)(2)-2,5](2) . 0.5PhH (I). Tetraphenylbismuth 2,5-dinitrophenoxide (II) has been synthesized by the reaction between complex I and pentaphenylbismuth and also via dephenylation of pentaphenylbismuth with 2,5-dintrophenol. The kinetically unstable tetraphenylbismuth bromide (III) is formed by the ligand redistribution reaction between pentaphenylbismuth and triphenylbismuth dibromide. The structures of complexes I-III have been characterized by X-ray diffraction. The bismuth atoms in complexes I-III have a distorted trigonal bipyramidal coordination, phenyl ligands are in the equatorial plane of a molecule of complex I (Bi-C, 2.196(5)-2.212(5) angstrom), and two aroxyl ligands are in its axial plane (Bi-O, 2.227(4), 2.228(3) angstrom). The oxygen atom of one of the ortho-nitro groups of the phenol residue is coordinated to the bismuth atom (Bi...O, 2.890(7) angstrom). In molecules of complexes II and III, the equatorial positions are occupied by phenyl ligands (Bi-C-eqv, 2.195(3)-2.200(3) angstrom (II), 2.188(4)-2.199(4) angstrom (III)), whereas the axial positions are occupied by phenyl and 2,5-dinitrophenoxide ligands (Bi-C-ax, 2.242(3) angstrom; Bi-O, 2.527(2) angstrom; OBiCax 175.55(9)degrees in II) and a phenyl ligand and a bromine atom (Bi-C-ax, 2.231(4) angstrom; Bi-Br, 3.139(2) angstrom; BrBiCax, 174.87(10)degrees in III).