Silylation of a hafnocene complex containing a strongly activated dinitrogen ligand, [(η5-C5H2-1,2,4-Me 3)2Hf]2(μ2,η2, η2-N2), by addition of CySiH3 resulted in N-Si and Hf-H bond formation and a compound poised for subsequent N2 cleavage. Warming the silane addition product to 75 ° triggered N-N scission, for which the requisite electrons were provided by silyl migration. Dinitrogen cleavage coupled to N-C bond formation was also accomplished by carbonylation of the silylated product, yielding an unprecedented μ-formamidide ([NC(H)O]2-) ligand. Subsequent treatment with HCl yielded free formamide, demonstrating that an important organic molecule can be synthesized from N2, CO, an organosilane, and protons.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry