Abstract
The insertion of CO(2) into metal hydrides and the microscopic reverse decarboxylation of metal formates are important elementary steps in catalytic cycles for both CO(2) 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 CO(2) insertion into transition metal hydrides. The investigation finds that the most effective method to accelerate the rate of CO(2) insertion into a metal hydride can be dependent on the nature of the rate-determining transition state (TS). We demonstrate that for an innersphere CO(2) insertion reaction, which is proposed to have a direct interaction between CO(2) and the metal in the rate-determining TS, the rate of insertion increases as the ancillary ligand becomes more electron rich or less sterically bulky. There is, however, no rate enhancement from Lewis acids (LA). In comparison, we establish that for an outersphere CO(2) insertion, proposed to proceed with no interaction between CO(2) and the metal in the rate-determining TS, there is a dramatic LA effect. Furthermore, for both inner- and outersphere reactions, we show that there is a small solvent effect on the rate of CO(2) insertion. Solvents that have higher acceptor numbers generally lead to faster CO(2) insertion. Our results provide an experimental method to determine the pathway for CO(2) insertion and offer guidance for rate enhancement in CO(2) reduction catalysis.