Lindley Brian M, Walden Andrew G, Brasacchio Ann Marie, Casuras Andrea, Lease Nicholas, Chen Chun-Hsing, Goldman Alan S, Miller Alexander J M
Department of Chemistry , University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599-3290 , USA . Email:
Oglethorpe University , Atlanta , Georgia 30319 , USA.
Chem Sci. 2019 Aug 20;10(40):9326-9330. doi: 10.1039/c9sc03076j. eCollection 2019 Oct 28.
A C-H bond activation strategy based on electrochemical activation of a metal hydride is introduced. Electrochemical oxidation of ( PCP)IrH ( PCP is [1,3-( BuPCH)-CH]) in the presence of pyridine derivatives generates cationic Ir hydride complexes of the type [( PCP)IrH(L)] (where L = pyridine, 2,6-lutidine, or 2-phenylpyridine). Facile deprotonation of [( PCP)IrH(2,6-lutidine)] with the phosphazene base -butylimino-tris(pyrrolidino)phosphorane, BuP(pyrr), results in selective C-H activation of 1,2-difluorobenzene (1,2-DFB) solvent to generate ( PCP)Ir(H)(2,3-CFH). The overall electrochemical C-H activation reaction proceeds at room temperature without need for chemical activation by a sacrificial alkene hydrogen acceptor. This rare example of undirected electrochemical C-H activation holds promise for the development of future catalytic processes.
介绍了一种基于金属氢化物电化学活化的C-H键活化策略。在吡啶衍生物存在下，(PCP)IrH（PCP为[1,3-(BuPCH)-CH]）的电化学氧化生成[(PCP)IrH(L)]类型的阳离子铱氢配合物（其中L = 吡啶、2,6-二甲基吡啶或2-苯基吡啶）。用磷腈碱丁基亚氨基三(吡咯烷基)磷烷，BuP(pyrr)对[(PCP)IrH(2,6-二甲基吡啶)]进行 facile 去质子化，导致1,2-二氟苯(1,2-DFB)溶剂发生选择性C-H活化，生成(PCP)Ir(H)(2,3-CFH)。整个电化学C-H活化反应在室温下进行，无需通过牺牲性烯烃氢受体进行化学活化。这种罕见的非定向电化学C-H活化实例为未来催化过程的发展带来了希望。
