Kinetic Studies of CO2 Insertion into Metal–Element σ-Bonds

Abstract

Despite the plethora of metal catalyzed reactions for CO₂ utilization that have been developed in academic laboratories, practical systems remain elusive. The understanding of the elementary steps in catalysis is a proven method to improve catalytic performance. In many catalytic cycles for CO₂ utilization, the insertion of CO₂ into a metal–element σ-bond, such as hydrides, alkyls, amides, or hydroxides, is a crucial step. However, despite the many demonstrations of CO₂ insertion, there are a paucity of kinetic studies, and information about the reaction mechanism has been predominantly elucidated from computational investigations. In this Account, kinetic studies on CO₂ insertion into late transition metal–element σ-bonds performed by my group are summarized, along with their implications for catalysis.