Unexpected reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 with diazoalkane and carbon disulfide: Activation and cleavage of the NN 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)[(η5-C5H3)Mo(CO)3]2 (1), which led to (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)2(O){μ–η1:η2-NC(RC6H3)(RC6H4)}] [R = H (2), p-Me (3)]. Two products (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(μ–η1:η2-CS)] (4) and (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(μ–η2:η2-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.

Graphical abstractThe thermal reactions of (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1) with diazoalkane Ar2CN2 led to the NN bond cleavage and an orthometalation of the aryl products. The reaction of complex 1 with CS2 afforded two products with the disproportionation of carbon disulfide.Figure optionsDownload full-size imageDownload as PowerPoint slide