化学
配体(生物化学)
钳子运动
氧化还原
芳基
钳形配体
偶联反应
试剂
催化循环
激进的
光化学
猝灭(荧光)
镍
催化作用
还原消去
组合化学
药物化学
有机化学
荧光
生物化学
烷基
受体
物理
量子力学
作者
Vikramjeet Singh,Harshit Jain,Shounak Nath,Debashis Adhikari
标识
DOI:10.1002/chem.202303189
摘要
Abstract The redox‐active nature of a pincer has been exploited to conduct C−C cross‐coupling reactions under mild conditions. A nickel complex with a NNN pincer was dimeric in the solid state, and the structure displayed a Ni 2 N 2 diamond core. In the dimeric structure, both ligand backbones house an electron, in the iminosemiquinonate form, to keep the metal's oxidation state at +2. In the presence of an aryl Grignard reagent, only 3 mol % loading the nickel complex generates a Kumada cross‐coupled product in good yield from a wide variety of aryl‐X (X= I, Br, Cl) substrates. That the ligand‐based radical remains responsible for promoting such a coupling reaction following a radical pathway is suggested by TEMPO quenching. Furthermore, a radical‐clock experiment along with tracing product distribution unambiguously supported the radical's involvement through the catalytic cycle. A series of thorough mechanistic probation, including computational DFT analysis, disclosed the cooperative action of both redox‐active pincer ligand and the metal centre to drive the reaction.
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