Effect of Nucleophilicity on the Kinetics of CO₂ Insertion into Pincer-Supported Nickel Complexes.

ABSTRACT: The insertion of CO₂ into metal-element σ-bonds such as M-H, M-OH, and M-NH₂ is often proposed to be a key step in catalytic CO₂ conversion. Nevertheless, there are few experimental studies measuring the kinetics of CO₂ insertion or comparing insertion into L_nM-E (E = H, OH, or NH₂) complexes with the same ancillary ligands. Here, we use a rapid mixing stopped-flow instrument to measure the rate of CO₂ insertion into (^tBuPCP)Ni(OH) (^tBuPCP = 2,6-C₆H₃(CH₂P^tBu₂)₂) and show that it proceeds at a faster rate than insertion into the corresponding metal hydride. We also demonstrate that the rate of CO₂ insertion into (

SUBMITTER: Heimann JE 

PROVIDER: S-EPMC12392925 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature