PHOSPHORUS ABSTRACTION REACTIONS RELATED TO HYDRODESULFURIZATION - FORMATION OF CP'2MO2CO2S3(CO)2(MU-3-PR) FROM CP'2MO2CO2S3(CO)4 AND PHOSPHINES

The cluster Cp'2Mo2Co2S3(CO)4 (1) (Cp' = C5H4Me) abstracts the phosphinidene group R-P at 80-degrees-C from phenylphosphine to form the cubane-like cluster Cp'2Mo2Co2S3(CO)2(mu-3-PPh) (4) probably via the phosphine adduct Cp'2Mo2Co2S3(CO)3(PH2Ph) (3). This is analogous to the desulfurization of thiols and thiophene by 1. Further reaction with the phosphine leads to the phosphine-substituted cubane Cp'2Mo2Co2(CO)(PH2Ph)S3(mu-3-PPh) (5). Reactions of 1 with diphenylphosphine are faster and form the monophosphine adduct as well as the cis and trans diadducts. Further reaction at 110-degrees-C with an excess of the phosphine does not give a clean reaction; however, some benzene is observed to form. Crystal data for 4: space group Pc2(1)n, Z = 4, a = 10.210 (2) angstrom, b = 12.767 (3) angstrom, c = 18.097 (4) angstrom, alpha = beta = delta = 90.000-degrees, V = 2358.8 (7) angstrom 3, R = 5.84, R(w) = 4.93 based on 1995 reflections with F0 greater-than-or-equal-to 0.6-sigma-(F).