SPONTANEOUS ISOMERIZATION OF SYMMETRICAL M(MU-NO)(2)M LINKAGES TO (ON)M=N=M=O GROUPINGS

{Treatment of Cp*Mo(NO)R(2) complexes (Cp* = eta(5)-C(5)Me(5); R = CH(2)CMe(3), CH(2)CMe(2)Ph) in C6H6 at 5 degrees C with H-2 results in the formation of [Cp*MoR](2)(mu-NO)(2) products (R = CH(2)CMe(3) (1), CH(2)CMe(2)Ph (2)) which are isolable in 25-30% yields. Similar treatment of an equimolar mixture of Cp*Mo(NO)(CH(2)SiMe(3))(2) and Cp*W(NO)(CH(2)SiMe(3))(2) with H-2 results in the formation of a heterobimetallic species, [Cp*Mo(CH(2)SiMe(3))](mu-NO)(2)[Cp*W(CH(2)SiMe(3))] (3). Complexes 1, 2, and 3 isomerize in solution at ambient temperatures To form [Cp*Mo-(NO)R](mu-N)[Cp*Mo(O)R] (R = CH(2)CMe(3) (4), CH(2)CMe(2)Ph (5)) and a 60:40 (M(1) = W:M(1) = Mo) mixture of [Cp*M(1)(NO)(CH(2)SiMe(3))](mu-N)[Cp*M(2)(O)(CH(2)SiM(3))] (6), respectively. The solid-state molecular structures of 1 and 6 have been established by single-crystal X-ray crystallographic analyses. Crystals of [Cp*Mo(CH(2)CMe(3))](2)-(mu-NO)(2) (1) are orthorhombic of space group Pbcn: a = 12.570(3) Angstrom