Different Modes of Reaction of Lithium Phosphides with Cp*M(NO)(X)Cl Complexes of Molybdenum and Tungsten

Abstract

Treatment of Cp*M(NO)(X)Cl complexes (M = Mo, W; X, = CH2SiMe3, CH2CMe3, NHCMe3, OCMe3, Cl) with lithium phosphides can result in one of three different types of reactions. Some reactions involve the starting material undergoing metathesis of a chloro ligand, and others effect reduction of the organometallic reactant, while a third class results in a scrambling of the ligands of the starting complex. Reactions of Cp*M(NO)(X)Cl with LiPPh2 lead to formation of the respective phosphido-containing complexes Cp*M(NO)(X)(PPh2) [M = W, X = CH2SiMe3 (1), CH2CMe3 (2), NHCMe3 (3), OCMe3 (4); M = Mo, X = NHCMe3 (5)]. In contrast, treatment of the molybdenum complexes Cp*Mo(NO)(X)Cl (X = CH2SiMe3, CH2CMe3, OCMe3) with LiPPh2 under identical conditions affords no isolable products. When metathesis of the chloro ligands in the Cp*M(NO)Cl2 complexes of Mo and W is attempted with either LiPPh2 or LiPPhH, the only isolable products formed are those resulting from the reduction of the organometallic reactant. Thus, treatm...