Acceleration of CO₂ insertion into metal hydrides: ligand, Lewis acid, and solvent effects on reaction kinetics.

ABSTRACT: The insertion of CO₂ into metal hydrides and the microscopic reverse decarboxylation of metal formates are important elementary steps in catalytic cycles for both CO₂ hydrogenation to formic acid and methanol as well as formic acid and methanol dehydrogenation. Here, we use rapid mixing stopped-flow techniques to study the kinetics and mechanism of CO₂ insertion into transition metal hydrides. The investigation finds that the most effective method to accelerate the rate of CO₂ insertion into a metal hydride can be dependent on the nature of the rate-determining transition state (TS). We demonstrate that for an innersphere CO₂ insertion reaction, which is proposed to have a direct interaction between CO₂ and the metal in the

SUBMITTER: Heimann JE 

PROVIDER: S-EPMC6115618 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature