Reversible Homolysis of a Carbon-Carbon σ-Bond Enabled by Complexation-Induced Bond-Weakening.

ABSTRACT: A case study of catalytic carbon-carbon σ-bond homolysis is presented. The coordination of a redox-active Lewis acid catalyst reduces the bond-dissociation free energies of adjacent carbon-carbon σ-bonds, and this complexation-induced bond-weakening is used to effect reversible carbon-carbon bond homolysis. Stereochemical isomerization of 1,2-disubstituted cyclopropanes was investigated as a model reaction with a ruthenium (III/II) redox couple adopted for bond weakening. Results from our mechanistic investigation into the stereospecificity of the isomerization reaction are consistent with selective complexation-induced carbon-carbon bond homolysis. The ΔG^‡ of catalyzed and uncatalyzed reactions were estimated to be 14.4 and 40.0 kcal/mol, respectively with the computatio

SUBMITTER: Kim S 

PROVIDER: S-EPMC9671280 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature