Synthesis and structure of '16-electron' rhodium(III) catalysts for transfer hydrogenation of a cyclic imine: mechanistic implications

摘要

Significant Rh-NH π-bonding in formally 16-electron (η~5-C_5Me_5)Rh(XNC_6H_4NX') (X, X' = H or Ts) is shown by structural features and by DFT calculations; (η~5-C_5Me_5)Rh(TsNC_6H_4NH) is the fastest transfer hydrogenation catalyst of the three complexes and generates a formate complex under catalytic conditions.