Kynman, Amy E. and Lau, Samantha and Dowd, Sean O. and Krämer, Tobias and Chaplin, Adrian B. (2020) Oxidative Addition of Biphenylene and Chlorobenzene to a Rh(CNC) Complex. European Journal of Inorganic Chemistry, 2020 (41). pp. 3899-3906. ISSN 1434-1948

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Abstract

The readily accessible rhodium(I) complex [Rh(CNC–Me)(SOMe2)][BArF4], featuring a NHC-based pincer ligand, is shown to undergo selective oxidative addition of the C–C bond of biphenylene and the C–Cl bond of chlorobenzene under mild conditions. 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].

Item Type:	Article
Keywords:	Oxidative Addition; Biphenylene; Chlorobenzene; Rh(CNC) Complex;
Academic Unit:	Faculty of Science and Engineering > Chemistry Faculty of Science and Engineering > Research Institutes > Hamilton Institute
Item ID:	16201
Identification Number:	https://doi.org/10.1002/ejic.202000780
Depositing User:	Tobias Kraemer
Date Deposited:	29 Jun 2022 08:29
Journal or Publication Title:	European Journal of Inorganic Chemistry
Refereed:	Yes
URI:	Publisher
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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