A novel Redox/Fission reaction of the molybdenum tetracarbonyl complex of 3-diphenylphosphino-(1R)-(+)-camphor dimethylhydrazone. Crystal structure of [Mo(CO)4(PPh2C10H15NH)]

This paper is dedicated to the outstanding chemist Professor Akio Yamamoto upon his retirement from the Tokyo Institute of Technology.
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Abstract

Treatment of the molybdenum tetracarbonyl complex of 3-diphenylphosphino-(1R)-(+)-camphor dimethylhydrazone [Mo(CO)4(PPh2C10H15NNMe2] (1a) with hydrogen chloride effects a rapid Redox/Fission reaction to give the molybdenum(II) imine complex [Mo(CO)3Cl2(PPh2C10H15NH)] (2a). Other strong acids HX reacted similarly to give analogous complexes [Mo(CO)3X2(PPh2C10H15NH)] (X = Br, I or OOCCF3). Reduction of 2a with sodium borohydride in the presence of carbon monoxide gave [Mo(CO)4(PPh2C10H15NH)] (1b), the crystal structure of which was determined. Treatment of 1b with LiN(SiMe3)2, followed by MeI gave [Mo(CO)4(PPh2C10H15NMe)] (1c). Treatment of 1a with bromine gave the tricarbonylmolybdenum(II) complex [Mo(CO)3Br2(PPh2C10H15NNMe2)] (2e). NMR and IR data, and bond length/bond angle data for 1b, are given.

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