ORGANOMETALLIC NITROSYL CHEMISTRY .54. REACTIONS OF 16-ELECTRON CP’M(NO)R2 COMPLEXES OF MOLYBDENUM AND TUNGSTEN WITH WATER

{The hydrolytic instability of Cp’Mo(NO)R2 complexes (Cp’ = Cp (eta-5-C5H5), Cp* (eta-5-C5Me5); R = alkyl, aryl) becomes evident during attempts to synthesize them by procedures which have previously afforded the congeneric tungsten species. Thus, treatment of Cp*Mo(NO)I2 with 2 equiv of Me3SiCH2MgCl in Et2O at room temperature results in the formation of three organometallic complexes which are separable by chromatography on alumina. These products are (a) the expected alkylation product, i.e. the 16-valence-electron dialkyl complex Cp*Mo(NO)(CH2SiMe3)2 (1), (b) a novel bimetallic bridging-oxo complex, [CP*Mo(NO)(CH2SiMe3)]2(eta-O) (2), formed by hydrolysis of 1 during workup, and (c) a dimeric reduction product of the starting material, namely [Cp*Mo(NO)I]2 (3). Each of the complexes 1-3 has been fully characterized by conventional spectroscopic methods, and a single-crystal X-ray crystallographic analysis of 2 has also been performed. Crystal data for 2: triclinic, space group P1BAR