LAUSR

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) Å), and two aroxyl ligands are in its axial plane (Bi–O, 2.227(4), 2.228(3) Å). 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) Å). In molecules of complexes II and III, the equatorial positions are occupied by phenyl ligands (Bi–Сeqv, 2.195(3)–2.200(3) Å (II), 2.188(4)–2.199(4) Å (III)), whereas the axial positions are occupied by phenyl and 2,5-dinitrophenoxide ligands (Bi–Сax, 2.242(3) Å; Bi–O, 2.527(2) Å; OBiCax 175.55(9)° in II) and a phenyl ligand and a bromine atom (Bi–Cax, 2.231(4) Å; Bi–Br, 3.139(2) Å; BrBiCax, 174.87(10)° in III).