Photogenerated Ni(I)-Bipyridine Halide Complexes: Structure-Function Relationships for Competitive C(sp²)-Cl Oxidative Addition and Dimerization Reactivity Pathways.

ABSTRACT: We report the facile photochemical generation of a library of Ni(I)-bpy halide complexes (Ni(I)(^Rbpy)X (R = t-Bu, H, MeOOC; X = Cl, Br, I) and benchmark their relative reactivity toward competitive oxidative addition and off-cycle dimerization pathways. Structure-function relationships between the ligand set and reactivity are developed, with particular emphasis on rationalizing previously uncharacterized ligand-controlled reactivity toward high energy and challenging C(sp²)-Cl bonds. Through a dual Hammett and computational analysis, the mechanism of the formal oxidative addition is found to proceed through an S_NAr-type pathway, consisting of a nucleophilic two-electron transfer between the Ni(I) 3d(z²) orbital and the C

SUBMITTER: Cagan DA 

PROVIDER: S-EPMC10330939 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature