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

Three cationic aryl−antimony and −bismuth complexes stabilized by intra- or intermolecular coordination have been prepared. Treatment of either SbAr 2 Cl or BiAr 2 Cl (Ar = 2-[(dimethylamino)methyl]phenyl, 2-(Me 2 NCH 2 )C 6 H 4 ) with TlPF 6 afforded [SbAr 2 ][PF 6 ] ( 1 ) or [BiAr 2 ][PF 6 ] ( 2 ), respectively. A related complex, [SbPh 2 {OP(NMe 2 ) 3 } 2 ][PF 6 ] ( 5 ), stabilized by intermolecular coordination, was prepared via the reaction of SbPhCl 2 with 2 equiv of TlPF 6 in the presence of an excess of OP(NMe 2 ) 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.