Metal-metal multiply-bonded complexes of technetium. 7. Oxidative decomposition of tetrachlorotetrakis(dimethylphenylphosphino)ditechnetium (II) by an aminium hexachloroantimonate(V)

TcCl4(PMe2Ph)(2) . 2SbCl(3) was isolated in low yield from the reaction of Tc2Cl4(PMe2Ph)(2) with 2 equiv. of [(p-BrC6H4)(3)N] [SbCl6] in acetonitrile. Single crystals were obtained by slow evaporation of a toluene solution. The: structure, determined by X-ray crystallography, is composed of infinite one-dimensional chains of an alternating sequence of TcCl4(PMe2Ph)(2) and (SbCl3)(2) molecules. The individual molecular species are loosely associated through Lewis acid-base interactions between the equatorial chlorine atoms of TcCl4(PMe2Ph)(2) and the individual SbCl3 units. The chains are continued by an additional weak Lewis acid-base interaction between neighboring SbCl3 molecules. The distorted pentagonal bipyramidal coordination geometry about the antimony atom is completed by a weak pi-interaction with the phenyl ring of TcCl4(PMe2Ph)(2). Crystal data for TcCl4(PNe2Ph)(2) . 2SbCl(3) (1) at 23 degrees C: M = 972.28, triclinic, <P(1)over bar> (No. 2), a = 10.591(3), b = 10.619(2), c = 7.578(1) Angstrom, a = 104.54(2), beta = 99.69(2), gamma = 69.92(2)degrees, V = 771.7(3) Angstrom(3), Z = 1. (C) 1998 Elsevier Science S.A.