Cationic Complexes of Antimony(III) and Bismuth(III) Stabilized by Intra- or Intermolecular Coordination

Abstract

Three cationic aryl−antimony and −bismuth complexes stabilized by intra- or intermolecular coordination have been prepared. Treatment of either SbAr2Cl or BiAr2Cl (Ar = 2-[(dimethylamino)methyl]phenyl, 2-(Me2NCH2)C6H4) with TlPF6 afforded [SbAr2][PF6] (1) or [BiAr2][PF6] (2), respectively. A related complex, [SbPh2{OP(NMe2)3}2][PF6] (5), stabilized by intermolecular coordination, was prepared via the reaction of SbPhCl2 with 2 equiv of TlPF6 in the presence of an excess of OP(NMe2)3. The X-ray crystal structures of compounds 1, 2, and 5 are described; the coordination geometry at the group 15 element center in each new compound was found to be distorted trigonal bipyramidal.