Carbon Monoxide-Induced Dinitrogen Cleavage with Group 4 Metallocenes: Reaction Scope and Coupling to N−H Bond Formation and CO Deoxygenation

The scope of CO-induced N(2) cleavage in a series of zirconocene and hafnocene complexes containing activated, side-on bound dinitrogen ligands has been studied. In each case, bridging oxamidide ligands, [N(2)C(2)O(2)](4-), were formed from N-N bond cleavage coupled to N-C and C-C bond assembly. For the zirconium examples, [(eta(5)-C(5)Me(4)H)(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) and [Me(2)Si(eta(5)-C(5)Me(4))(eta(5)-C(5)H(3)-3-(t)Bu)Zr](2)(mu(2),eta(2),eta(2)-N(2)), dinitrogen loss became competitive with N(2) carbonylation, and significant quantities of the zirconocene dicarbonyl accompanied oxamidide formation. In contrast, the hafnocene complex [(eta(5)-C(5)Me(4)H)(2)Hf](2)(mu(2),eta(2),eta(2)-N(2)) underwent clean carbonylative dinitrogen cleavage with no evidence of N(2) loss. CO-induced N(2) cleavage was also coupled to N-H bond formation by hydrogenation and C-H bond activation, as carbonylation of the zirconocene and hafnocene dinitrogen complexes in the presence of H(2) or phenylacetylene furnished isocyanato metallocene complexes with bridging imido (mu-NH) ligands. In the case of the ansa-hafnocene dinitrogen complex, replacing the dihydrogen atmosphere with various primary silanes yielded an isocyanato hafnocene mu-oxo hydride resulting from cleavage of N(2) and CO, the diatomics with the two strongest bonds in chemistry.