ROLE OF [CP (STAR) MO(MU-S)]2S2CH2 IN DICHLOROMETHANE HYDROGENOLYSIS

The reaction of (Cp*MoS)2S2CH2 (Cp* = C5Me5) with dichloromethane under 1-2 atm of H-2 at 50-degrees-C led to the hydrogenolysis of dichloromethane and the formation of (Cp*MoS2CH2)2 (1). Complex 1 crystallized in space group P1BAR with unit cell dimensions a = 7.992 (2) angstrom, b = 8.354 (3) angstrom, c = 10.624 (5) angstrom, alpha = 88.11 (3)-degrees, beta = 74.15 (3)-degrees, gamma = 62.83 (2)-degrees, and V = 603.6 (4) angstrom 3. The X-ray diffraction study of 1 verified that the two Cp*Mo units were symmetrically bridged by two eta-2 methanedithiolate ligands. When (Cp*MoS)2S2CH2 was reacted with dichloromethane under nitrogen rather than hydrogen pressure, the cationic product [(Cp*Mo)2-(S2CH2)(mu-S)(mu-SCH2Cl)]Cl (2) was formed. Complex 2 reacted with hydrogen to form 1 and is, therefore, a likely intermediate in the dichloromethane hydrogenolysis.