Unexpected reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with diazoalkane and carbon disulfide:: Activation and cleavage of the N=N bond and disproportionation of carbon disulfide

The N-N bond cleavage of diazoalkane Ar2CN2 following a orthometalation of the aryl occurred in the thermal reactions with (Me2C)(Me2Si)[(eta(5)-C5H3)Mo(CO)(3)](2) (1), which led to (Me2C)( Me2Si)[(eta 5-C5H3)Mo-2(CO)(2)(O){mu- eta(1):eta(2)-N = C(RC6H3)(RC6H4)}] [R = H (2), p-Me ( 3)]. Two products (Me2C)(Me2Si)[(eta(5)-C5H3)(2)Mo-2(CO)(4)(mu-eta(1):eta(2)-CS)] (4) and (Me2C)(Me2Si)[(eta(5)-C5H3)(2)Mo-2 (CO)(4)(mu-eta(2):eta(2)-CS3)] (5) were isolated in the reaction of complex 1 with CS2 with the disproportionation of carbon disulfide. The molecular structures of 2-5 have been determined by X-ray diffraction analysis. The proposed mechanism was discussed. (c) 2007 Elsevier B. V. All rights reserved.