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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)][BAr^F ₄], 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)][BAr^F ₄] and [Rh(CNC-Me)(Ph)Cl(OSMe₂)][BAr^F ₄], 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)][BAr^F ₄].

SUBMITTER: Kynman AE

PROVIDER: S-EPMC7702176 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Oxidative Addition of Biphenylene and Chlorobenzene to a Rh(CNC) Complex.

Kynman Amy E AE Lau Samantha S Dowd Sean O SO Krämer Tobias T Chaplin Adrian B AB

European journal of inorganic chemistry 20201020 41

The synthesis and organometallic chemistry of rhodium(I) complex [Rh(CNC-Me)(SOMe2)][BArF 4], 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)][BArF 4] and [Rh(CNC-Me)(Ph)Cl(OSMe2)][BArF 4], respectively. A d ...[more]

PMID: 33328794

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