Carbonylhydridonitrosyltris(trimethylphosphine)molybdenum(0): An Activated Hydride Complex

Abstract

The synthesis of the mer-Mo(CO)H(NO)(PMe3)3 complex 3 is described, which is obtained from Mo(CO)4(NO)AlCl4 via the isolable intermediates MoCl(CO)(NO)(PMe3)3 (1) and the borohydride complex Mo(η1-BH4)(CO)(NO)(PMe3)3 (2). The reactivity of 3 with respect to insertions has been probed. 3 thus reacts with benzaldehyde, benzophenone, acetophenone, and acetone to afford the corresponding alkoxide complexes Mo(CO)(NO)(PMe3)3(OCHR‘R‘‘) (R‘ = H, R‘‘ = Ph (4a); R‘, R‘‘ = Ph (4b); R‘ = Me, R‘‘ = Ph (4c), and R‘, R‘‘ = Me (4d)). A high propensity of 3 to undergo carbonyl insertion was also manifested in its transformations with CO2 and metal carbonyl compounds. The conversion of 3 with CO2 leads to the formato-O-complex Mo(CO)(NO)(PMe3)3(OCHO) (5), while CO induces PMe3 substitution with formation of the nonisolable Mo(CO)2(NO)(PMe3)2H compound (6). Fe(CO)5 readily inserts to yield the dinuclear formyl species (Me3P)3(ON)(OC)Mo(μ-OCH)Fe(CO)4 (7a), and Re2(CO)10 is transformed to the related μ-formyl complex (Me3P)3...