Functionalization of hafnium oxamidide complexes prepared from CO-induced N2 cleavage

Functionalization of the nitrogen atoms in the hafnocene oxamidide complexes [Me(2)Si(η(5)-C(5)Me(4))(η(5)-C(5)H(3)-3-(t)Bu)Hf](2)(N(2)C(2)O(2)) and [(η(5)-C(5)Me(4)H)(2)Hf](2)(N(2)C(2)O(2)), prepared from CO-induced N(2) bond cleavage, was explored by cycloaddition and by formal 1,2-addition chemistry. The ansa-hafnocene variant, [Me(2)Si(η(5)-C(5)Me(4))(η(5)-C(5)H(3)-3-(t)Bu)Hf](2)(N(2)C(2)O(2)), undergoes facile cycloaddition with heterocumulenes such as (t)BuNCO and CO(2) to form new N-C and Hf-O bonds. Both products were crystallographically characterized, and the latter reaction demonstrates that an organic ligand can be synthesized from three abundant and often inert small molecules: N(2), CO, and CO(2). Treatment of [Me(2)Si(η(5)-C(5)Me(4))(η(5)-C(5)H(3)-3-(t)Bu)Hf](2)(N(2)C(2)O(2)) with I(2) yielded the monomeric iodohafnocene isocyanate, Me(2)Si(η(5)-C(5)Me(4))(η(5)-C(5)H(3)-3-(t)Bu)Hf(I)(NCO), demonstrating that C-C bond formation is reversible. Alkylation of the oxamidide ligand in [(η(5)-C(5)Me(4)H)(2)Hf](2)(N(2)C(2)O(2)) was explored due to the high symmetry of the complex. A host of sequential 1,2-addition reactions with various alkyl halides was discovered and both N- and N,N'-alkylated products were obtained. Treatment with Brønsted acids such as HCl or ethanol liberates the free oxamides, H(R(1))NC(O)C(O)N(R(2))H, which are useful precursors for N,N'-diamines, N-heterocyclic carbenes, and other heterocycles. Oxamidide functionalization in [(η(5)-C(5)Me(4)H)(2)Hf](2)(N(2)C(2)O(2)) was also accomplished with silanes and terminal alkynes, resulting in additional N-Si and N-H bond formation, respectively.