Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
J Am Chem Soc. 2011 Jul 13;133(27):10406-9. doi: 10.1021/ja2042595. Epub 2011 Jun 17.
Silylation of a hafnocene complex containing a strongly activated dinitrogen ligand, (η(5)-C(5)H(2)-1,2,4-Me(3))(2)Hf(μ(2),η(2),η(2)-N(2)), by addition of CySiH(3) resulted in N-Si and Hf-H bond formation and a compound poised for subsequent N(2) cleavage. Warming the silane addition product to 75 °C 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) ligand. Subsequent treatment with HCl yielded free formamide, demonstrating that an important organic molecule can be synthesized from N(2), CO, an organosilane, and protons.
用三甲基硅烷（CySiH3）对含有强活化二氮配体的二核铪配合物(η(5)-C(5)H(2)-1,2,4-Me(3))(2)Hf(μ(2),η(2),η(2)-N(2))进行硅烷化，导致形成 N-Si 和 Hf-H 键，并生成一个有利于随后进行 N(2)裂解的化合物。将硅烷加成产物加热至 75°C 会引发 N-N 键的断裂，所需的电子由硅烷基迁移提供。通过对硅烷化产物进行羰基化反应，也可以实现二氮的裂解和 N-C 键的形成，生成了前所未有的 μ-甲酰胺(NC(H)O)配体。随后用 HCl 处理得到游离的甲酰胺，这表明可以从 N(2)、CO、有机硅烷和质子合成重要的有机分子。
