Stevens Jeremiah E, Moore Curtis E, Thomas Christine M
Department of Chemistry and Biochemistry, The Ohio State University, 100 W. 18th Avenue, Columbus, Ohio 43210, United States.
J Am Chem Soc. 2023 Jan 18;145(2):794-799. doi: 10.1021/jacs.2c12157. Epub 2023 Jan 3.
Despite the utility of Si-Si bonds, there are relatively few examples of Si-Si bond formation by base metals. In this work, a four-coordinate iron complex, (PNNP)Fe, is shown to strongly activate the Si-H bonds in primary silanes across the Fe-amide bonds in a metal-ligand cooperative fashion. Upon treatment with excess silane, Si-Si dehydrogenative homocoupling is shown to occur across the Fe-N bond without concomitant oxidation and spin state changes at the Fe center.
尽管硅-硅键具有实用性,但碱金属形成硅-硅键的例子相对较少。在这项工作中,一种四配位铁配合物(PNNP)Fe被证明能以金属-配体协同的方式,通过铁-酰胺键强烈活化伯硅烷中的硅-氢键。在用过量硅烷处理时,硅-硅脱氢均偶联反应被证明是通过铁-氮键发生的,同时铁中心没有伴随氧化和自旋态变化。