硼烷
硼烷
氢化物
化学
硼酸化
催化作用
双功能
配体(生物化学)
组合化学
氨硼烷
铑
均相催化
有机化学
硼
金属
芳基
制氢
受体
生物化学
烷基
作者
Macarena G. Alférez,Juan J. Moreno,Miguel A. Gaona,Celia Maya,Jesús Campos
标识
DOI:10.1021/acscatal.3c02764
摘要
The incorporation of boron functionalities into transition-metal catalysts has become a promising strategy to improve catalytic performance, although their synthesis typically entails the preparation of sophisticated bifunctional ligands. We report here the facile and direct postsynthetic functionalization of rhodium(I) compound [(η5-C9H7)Rh(PPh3)2] (1) by treatment with perfluorinated boranes. Borane addition to 1 results in an unusual C(sp2)-H hydride migration from the indenyl ligand to the metal with the concomitant formation of a C–B bond. In the case of Piers' borane [HB(C6F5)2], this is followed by a subsequent hydride migration that leads to an unprecedented 1,2-hydrogen shift reminiscent of Milstein's cooperative dearomatization pathways. Computational investigations provide a mechanistic picture for the successive hydride-migration steps, which enriches the non-innocent chemistry of widespread indenyl ligands. Moreover, we demonstrate that the addition of Piers' borane is highly beneficial for catalysis, increasing catalyst efficiency up to 3 orders of magnitude.
科研通智能强力驱动
Strongly Powered by AbleSci AI