金属催化氢化反应机制中缺失的一环：用于Co(-I)催化氢化反应的Co(-I)/Co(0)/Co(+I)催化循环
A Missing Piece of the Mechanism in Metal-Catalyzed Hydrogenation: Co(-I)/Co(0)/Co(+I) Catalytic Cycle for Co(-I)-Catalyzed Hydrogenation.
作者信息
Wu Song-Bai, Zhang Tonghuan, Chung Lung Wa, Wu Yun-Dong
机构信息
Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics , Peking University Shenzhen Graduate School , Shenzhen 518055 , China.
Department of Chemistry and Shenzhen Grubbs Institute , Southern University of Science and Technology , Shenzhen 518055 , China.
出版信息
Org Lett. 2019 Jan 18;21(2):360-364. doi: 10.1021/acs.orglett.8b03463. Epub 2019 Jan 2.
Hydrogenation catalyzed by unusually low-valent Co(-I) and Fe(-I) catalysts were recently reported. In contrast to the classical M(I)/M(III) (M = Rh or Ir) or Ir(III)/Ir(V) catalytic cycles in the singlet state (adiabatic reactions) for Rh- or Ir-catalyzed hydrogenation, our systematic DFT study elucidates a new Co(-I)/Co(0)/Co(+I) catalytic cycle involving both singlet and triplet states (nonadiabatic reaction). Also, the more electron-rich cobalt center of the Co(-I) catalyst was found to contribute higher reactivity for alkene hydrogenation.
最近报道了由异常低价的Co(-I)和Fe(-I)催化剂催化的氢化反应。与Rh或Ir催化氢化反应中经典的单重态M(I)/M(III)（M = Rh或Ir）或Ir(III)/Ir(V)催化循环（绝热反应）不同，我们系统的密度泛函理论（DFT）研究阐明了一个涉及单重态和三重态的新的Co(-I)/Co(0)/Co(+I)催化循环（非绝热反应）。此外，发现Co(-I)催化剂中电子密度更高的钴中心对烯烃氢化反应具有更高的反应活性。
Zotero 插件