First‐Row Transition‐Metal Complexes with Tetra‐Amido Macrocyclic Ligands for Water and C(sp³)−H Bond Oxidation: Performance Benchmarking Using Free Energy Relationships

Abstract

The catalytic oxidation of water and C(sp3)‐H bonds enables the conversion of solar/electrochemical energy into chemical energy and alcohol fuel production, respectively, and therefore plays important roles in energy conversion/storage. These transformations are typically catalyzed by the highly active complexes of the earth‐abundant first‐row transition metals (Mn, Fe, Co, Ni, and Cu) with tetra‐amido macrocyclic ligands (TAMLs), although the related kinetics and thermodynamics remain underexplored. This review uses free energy relationships between kinetic and thermodynamic descriptors as normalized metrics to benchmark/compare these TAML‐based catalysts and assess the advances in their development.