Triarylbismuth Dicarboxylates Ar3Bi[OC(O)R]2, Ar = p-Tol, R = CH2Cl; Ar = Ph, R = C6H4OMe-2, CH=CHPh

Abstract

Triarylbismuth dicarboxylates Ar₃Bi[OC(O)R]₂, Ar = p-Tol, R = CH₂Cl (I); Ar = Ph, R = C₆H₄OMe-2 (II), CH=CHPh (III) have been synthesized by the reactions of tri(para-tolyl)bismuth with monochloroacetic acid and triphenylbismuth with 2-methoxybenzoic and cinnamic acids in methyl-tert-butyl ether in the presence of tert-butyl hydroperoxide with a high yield. The Bi atoms in complexes I–III have a distorted trigonal bipyramidal coordination with carboxylate ligands in axial positions (OBiO angles, 171.06(6)° (I), 170.46(12)° (II), 175.39(8)° (III)). The Sb-O and Sb-C bond lengths are 2.283(2), 2.288(2) Å and 2.185(2)–2.199(2) Å (I), 2.265(7), 2.268(7) Å and 2.194(7)–2.218(8) Å (II), and 2.310(2), 2.310(2) Å and 2.200(2)–2.210(3) Å (III). Molecules of complexes I–III have intramolecular contacts between the Bi atom and the O atoms of carbonyl groups: the Bi⋯O(=C) distances are 2.990(2), 2.985(3) Å (I), 2.753(8), 2.739(8) Å (II), and 2.688(2) Å (III). The structural organization in crystals of complexes I–III is caused by weak inter-molecular hydrogen bonds H⋯O of 2.61–2.65 Å (I), 2.47–2.50 Å (II), and 2.56 Å (III).