Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, 637371, Singapore.
Department of Applied Chemistry, National Chiayi University, Chiayi, 60004, Taiwan.
Chemistry. 2018 Sep 25;24(54):14329-14334. doi: 10.1002/chem.201803410. Epub 2018 Sep 14.
The synthesis of a dimeric base-stabilized cobaltosilylene complex and its catalytic reactions are described. Treatment of the amidinato silicon(I) dimer [LSi:] (1; L=PhC(NtBu) ) with CoBr in toluene for 10 days afforded the dimeric amidinato cobaltosilylene [(LSi)μ-{CoBr(LSiBr)}] (2), which is speculated to proceed via "LSiCoBr" and "LSiBr" intermediates in the reaction. Compound 2 is paramagnetic, with an effective magnetic moment of 2.8 μB. Its electronic structure was elucidated by single-crystal X-ray crystallography and DFT studies. It was capable of catalyzing C-H bond functionalization, in which a combination of 2, phosphine and MeMgI can regio- and stereoselectively promoted the addition of the C≡C triple bonds in alkynes to the ortho-C-H position in arylpyridines. In addition, compound 2 catalyzed Kumada-type coupling reactions between aryl chlorides and the Grignard reagent 2-mesitylmagnesium bromide.
描述了一种二聚碱基稳定的钴硅烯配合物的合成及其催化反应。用 CoBr 在甲苯中处理亚胺硅（I）二聚体[LSi:]（1；L=PhC（NtBu））10 天，得到二聚亚胺钴硅烯[(LSi)μ-{CoBr(LSiBr)}]（2），反应推测通过“LSiCoBr”和“LSiBr”中间体进行。化合物 2 具有顺磁性，有效磁矩为 2.8μB。通过单晶 X 射线晶体学和 DFT 研究阐明了其电子结构。它能够催化 C-H 键官能化，其中 2、膦和 MeMgI 的组合可以区域和立体选择性地促进炔烃中的 C≡C 三键在芳基吡啶的邻位-C-H 位置的加成。此外，化合物 2 还催化芳基氯和 Grignard 试剂 2-三甲基金格氏溴之间的 Kumada 型偶联反应。
