Chloride metathesis or nitrosyl N-O bond cleavage in Cp(*)W(NO)(CH(2)SiMe(3))Cl upon treatment with alkali-metal alkoxides

The bimetallic compound [Cp*W(NO)(CH(2)SiMe(3))](mu(2)-eta(1):eta(2)-NC{H}SiMe(3))[Cp*W(Cl)(O)]( 1), is produced in low yield by the heterogeneous reaction between Cp*W(NO)(CH(2)SiMe(3))Cl and KOCMe(3) in pentane. However, when this reaction is performed in THF or Et(2)O, the expected metathesis product, Cp*W(NO)(CH(2)SiMe(3))(OCMe(3)), is obtained. When Cp*W(NO)(CH(2)SiMe(3))Cl is treated with KOMe in pentane, a different bimetallic compound, [Cp*W(No)(CH(2)SiMe(3))Cl](mu-N)[Cp*W(Cl)(eta(2)-N{O}{H}CH(2)SiMe(3))] (2), is produced along with the known dioxo alkyl complex Cp*W(NO)(CH(2)SiMe(3)). Again, the expected alkyl alkoxide product, Cp*W(NO)(CH(2)SiMe(3))(OMe), is produced when the reaction is effected in THF or Et(2)O. The roles of KOCMe(3) or KOMe during the formation of complexes 1 and 2 are presently unclear. However, when the reactions are performed using the Li or Na alkoxide salts, the expected metathesis products, namely the alkyl alkoxide complexes, are indeed produced. The solid-state molecular structures of bimetallic complexes 1 and 2 have been established by single-crystal X-ray crystallographic analyses.