DEGRADATION AND OXIDATION OF 1,1,1-TRICHLOROETHANE-MEDIATED RHODIUM COMPOUNDS - A NEW ENTRY IN THE SYNTHESIS OF BRIDGING VINYLIDENE AND ETA(1)-CHLOROVINYL COMPLEXES

1,1,1-Trichloroethane reacts with [Rh(HBiIm)(CNBu(t))(2)] and [Rh(mu-p z)(CNBu(t))(2)](2) (H(2)BiIm = 2,2'-biimidazole, pz = pyrazolate) to g ive [RhCl(eta(1)-CCl=CH2)(HBiIm)(CNBu(t))(2)] and [{Rh(mu-pz)Cl(CNBu(t ))(2)}(2)(mu-C=CH2)] respectively with spontaneous elimination. of HCl . Further reaction of the vinylidene-bridged compound with HBF4 and ox ygen gives the acyl complex mu-pz)(CNBu(t))(2)}(2)(mu-Cl)Cl(eta(1)-COC H3)]BF4, which constitutes, on. the whole, a model for the degradation and oxidation of organic chlorocarbons.