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

Chien-Wen Lin, Yu-Wei Chuang, Kuan-Yu LuYu-Heng Wang
ChemCatChem
2024

摘要

C(sp3)−H oxidation;homogeneous catalysis;linear free energy relationships;tetra-amido macrocyclic ligands (TAMLs);water oxidation Catalysis Physical and Theoretical Chemistry Organic Chemistry Inorganic Chemistry

The catalytic oxidation of water and C(sp 3 )−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.

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