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在阳离子（η-CMe）Ir（III）中心通过碱促进的远程C-H活化，涉及结合的CMe的可逆C-C键形成。

Base-Promoted, Remote C-H Activation at a Cationic (η-CMe)Ir(III) Center Involving Reversible C-C Bond Formation of Bound CMe.

作者信息

Moreno Juan J, Espada María F, Campos Jesús, López-Serrano Joaquín, Macgregor Stuart A, Carmona Ernesto

机构信息

Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA) , Universidad de Sevilla and Consejo Superior de Investigaciones Científicas (CSIC) , Avenida Américo Vespucio 49 , 41092 Sevilla , Spain.

Institute of Chemical Sciences , Heriot-Watt University , Edinburgh EH14 4AS , United Kingdom.

出版信息

J Am Chem Soc. 2019 Feb 13;141(6):2205-2210. doi: 10.1021/jacs.8b11752. Epub 2019 Feb 5.

DOI:10.1021/jacs.8b11752
PMID:30682245
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6396953/
Abstract

C-H bond activation at cationic [(η-CMe)Ir(PMeAr')] centers is described, where PMeAr' are the terphenyl phosphine ligands PMeAr and PMeAr. Different pathways are defined for the conversion of the five-coordinate complexes [(η-CMe)IrCl(PMeAr')], 2(Xyl) and 2(Dipp), into the corresponding pseudoallyls 3(Xyl) and 3(Dipp). In the absence of an external Brønsted base, electrophilic, remote ζ C-H activation takes place, for which the participation of dicationic species, [(η-CMe)Ir(PMeAr')], is proposed. When NEt is present, the PMeAr system is shown to proceed via 4(Dipp) as an intermediate en route to the thermodynamic, isomeric product 3(Dipp). This complex interconversion involves a non-innocent CMe ligand, which participates in C-H and C-C bond formation and cleavage. Remarkably, the conversion of 4(Dipp) to 3(Dipp) also proceeds in the solid state.

摘要

描述了阳离子[(η-CMe)Ir(PMeAr')]中心的C-H键活化，其中PMeAr'是三联苯膦配体PMeAr和PMeAr。定义了将五配位配合物[(η-CMe)IrCl(PMeAr')]、2(Xyl)和2(Dipp)转化为相应的准烯丙基3(Xyl)和3(Dipp)的不同途径。在没有外部布朗斯特碱的情况下，发生亲电远程ζ C-H活化，为此提出了二价阳离子物种[(η-CMe)Ir(PMeAr')]的参与。当存在NEt时，PMeAr体系显示通过4(Dipp)作为中间体生成热力学异构体产物3(Dipp)。这种配合物的相互转化涉及一个非惰性的CMe配体，它参与C-H和C-C键的形成与断裂。值得注意的是，4(Dipp)到3(Dipp)的转化也在固态下进行。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/284da9277929/ja-2018-117524_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/8298d7dfda73/ja-2018-117524_0004.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/bcb9104a47be/ja-2018-117524_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/65da79a08804/ja-2018-117524_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/c53f531fd058/ja-2018-117524_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/284da9277929/ja-2018-117524_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/8298d7dfda73/ja-2018-117524_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/884e49298f68/ja-2018-117524_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/1513ed2bdaaa/ja-2018-117524_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/bcb9104a47be/ja-2018-117524_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/65da79a08804/ja-2018-117524_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/c53f531fd058/ja-2018-117524_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ca46/6396953/284da9277929/ja-2018-117524_0003.jpg

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