@article{604f519cc23b4bed90b6b30bf1b19722,
title = "Oxidative Addition of Biphenylene and Chlorobenzene to a Rh(CNC) Complex",
abstract = "The synthesis and organometallic chemistry of rhodium(I) complex [Rh(CNC–Me)(SOMe2)][BArF4], featuring NHC-based pincer and labile dimethyl sulfoxide ligands, is reported. This complex reacts with biphenylene and chlorobenzene to afford products resulting from selective C–C and C–Cl bond activation, [Rh(CNC–Me)(2,2'-biphenyl)(OSMe2)][BArF4] and [Rh(CNC–Me)(Ph)Cl(OSMe2)][BArF4], respectively. A detailed DFT-based computational analysis indicates that C–H bond oxidative addition of these substrates is kinetically competitive, but in all cases endergonic: contrasting the large thermodynamic driving force calculated for insertion of the metal into the C–C and C–Cl bonds, respectively. Under equivalent conditions the substrates are not activated by the phosphine-based pincer complex [Rh(PNP-iPr)(SOMe2)][BArF4].",
keywords = "Computational analysis, DFT calculations, Oxidative addition, Pincer ligands, Rhodium",
author = "Kynman, \{Amy E.\} and Samantha Lau and Dowd, \{Sean O.\} and Tobias Kr{\"a}mer and Chaplin, \{Adrian B.\}",
note = "Funding Information: We thank the European Research Council (ERC, grant agreement 637313; A. E. K., S. L., A. B. C.) and Royal Society (UF100592, UF150675, A. B. C.) for financial support. T. K. acknowledges the DJEI/DES/SFI/HEA Irish Centre for High‐End Computing (ICHEC) for the provision of computational facilities and support. High‐resolution mass‐spectrometry data were collected using instruments purchased through support from Advantage West Midlands and the European Regional Development Fund. Crystallographic data were collected using an instrument that received funding from the ERC under the European Union's Horizon 2020 research and innovation programme (grant agreement No 637313). Funding Information: We thank the European Research Council (ERC, grant agreement 637313; A. E. K., S. L., A. B. C.) and Royal Society (UF100592, UF150675, A. B. C.) for financial support. T. K. acknowledges the DJEI/DES/SFI/HEA Irish Centre for High-End Computing (ICHEC) for the provision of computational facilities and support. High-resolution mass-spectrometry data were collected using instruments purchased through support from Advantage West Midlands and the European Regional Development Fund. Crystallographic data were collected using an instrument that received funding from the ERC under the European Union's Horizon 2020 research and innovation programme (grant agreement No 637313). Publisher Copyright: {\textcopyright} 2020 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH",
year = "2020",
month = nov,
day = "8",
doi = "10.1002/ejic.202000780",
language = "English",
volume = "2020",
pages = "3899--3906",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
number = "41",
}