A novel Redox/Fission reaction of the molybdenum tetracarbonyl complex of 3-diphenylphosphino-(1 R)-(+)-camphor dimethylhydrazone. Crystal structure of [ [formula omitted]H)

Abstract

Treatment of the molybdenum tetracarbonyl complex of 3-diphenylphosphino-(1 R)-(+)-camphor dimethylhydrazone [ Mo(CO) 4(PPh 2C 10H 15N NMe 2] ( 1a) with hydrogen chloride effects a rapid Redox/Fission reaction to give the molybdenum(II) imine complex [ Mo(CO) 3Cl 2(PPh 2C 10H 15N H)] ( 2a). Other strong acids HX reacted similarly to give analogous complexes [ Mo(CO) 3X 2(PPh 2C 10H 15N H)] (X = Br, I or OOCCF 3). Reduction of 2a with sodium borohydride in the presence of carbon monoxide gave [ Mo(CO) 4(PPh 2C 10H 15N H)] ( 1b), the crystal structure of which was determined. Treatment of 1b with LiN(SiMe 3) 2, followed by MeI gave [ Mo(CO) 4(PPh 2C 10H 15N Me)] ( 1c). Treatment of 1a with bromine gave the tricarbonylmolybdenum(II) complex [ Mo(CO) 3Br 2(PPh 2C 10H 15N NMe 2)] ( 2e). NMR and IR data, and bond length/bond angle data for 1b, are given.