Syntheses and reactivity of molybdenum complexes containing the diphenylphosphinodithioformato ligand

Abstract

Treatment of [Et 4N][Mo(CO)5(PPh 2)] ( 1) with CS 2 afforded [Et 4N][Mo(CO) 5(PPh 2CS 2)] ( 3) which was also synthesized from the reaction of Mo(CO) 5(CH 3CN) with [Et 4N][PPh 2CS 2] ( 2). In complex 3, the diphenylphosphinodithioformato ligand, PPh 2CS 2 −, coordinated to the molybdenum through the phosphorus atom. The reactions of 3 with various alkyl halides yielded the neutral complexes Mo(CO) 5[PPh 2(CS 2R)] (R=C 2H 5, C 2H 4OH, C 3H 5, 4– 6). Acylation of 3 with 1-naphthoyl chloride [C 10H 7C(O)Cl] gave the complex Mo(CO) 5[PPh 2(CS 2COC 10H 7)] ( 7) with moderate yield. Alkylation and acylation reactions occurred at the sulfur atom. Complex 3 reacted with CH 2I 2 to give the dinuclear complex [Mo(CO) 5(PPh 2CS 2)] 2( μ-CH 2) ( 8) in which the two metal atoms are bridged by the bidentate phosphorus ligand. Decarbonylation of 3 in CH 3CN produced an anionic product which was identified as [Et 4N][Mo(CO) 4(PPh 2CS 2)] ( 9). The PPh 2CS 2 − ligand of 9 bound to the metal center through both the phosphorus and one of the sulfur atoms. All of the complexes are identified by spectroscopic methods.