ORGANOMETALLIC AMIDO NITROSYL COMPLEXES OF MOLYBDENUM AND TUNGSTEN

{Treatment of Cp*M(NO)Cl2 (Cp* = eta5-C5Me5; M = Mo, W) with arylamines, ArNH2 (Ar = phenyl, o-tolyl, or p-tolyl) affords 18-valence-electron adducts of the type Cp*M(NO)Cl2.NH2-Ar. These adducts can be dehydrohalogenated with a strong base to produce the amido chloro complexes Cp*M(NO)(NHAr)Cl in good yields. These latter complexes can also be prepared by treatment of Cp*M(NO)Cl2 with 1 equiv of a lithium amide. Interestingly, treatment of Cp*M(NO)Cl2 with excess primary alkylamines produces directly the amido chloro complexes, Cp*M(NO)(NHR)CI(R=alkyl). Mixed alkyl amido and alkoxo amido complexes are preparable by sequential treatment of Cp*M(NO)Cl2 with 1 equiv of an alkylating reagent or lithium alkoxide followed by treatment with excess alkylamine. The solid-state molecular structures of the two representative complexes, Cp*Mo(NO)Cl2.PhNH2 (1) and Cp*W(NO)(OCMe3)-(NHCMe3) (18) have been established by single-crystal X-ray diffraction analyses. Crystals of 1 are monoclinic, space group P2(1)/c, with a = 8.590(1) angstrom