Syntheses and structures of dinuclear molybdenum complexes containing reactive .mu.-thiolate-thioether ligands

Abstract

Certain thiolate-bridged cationic complexes of the formula [(CpMo) 2 (S 2 CH 2 )(μ-S)(μ-SR)]SO 3 CF 3 react reversibly with olefins: The resulting adduct contains a thiolate-thioether bridging ligand. The stability of the olefin adduct varies significantly as the R substituent on the thiolate ligand and the substituents on the olefin and varied. The reaction of allene with [(CpMo) 2 (S 2 CH 2 )(μ-S)(μ-SR)]SO 3 CF 3 , where R=2-propenyl, led to the formation of an isolable thiolate-thioether complex, [(CpMo) 2 (S 2 CH 2 )(SC(=CH 2 )CH 2 SC(CH 3 )(=CH 2 ))]SO 3 CF 3 (3). The reaction of [(CpMo) 2 (S 2 CH 2 )(μ-S)(μ-SR)]SO 3 CF 3 (2; R=tert-butyl) with acetylene led to the isolation of a product of the formula [(CpMo)(SCH=CHSCMe 3 )(S 2 CH 2 )-MoCp]SO 3 CF 3 (4). X-ray structures of 4 and 3