Redox Potentials for the Synthesis of Cationic Transition Metal Complexes from the Metal and Weak Ligands: A Computational Methodology for Practical Oxidant Choice

In this work, a computational methodology for the estimation of the redox potentials necessary to synthesize transition metal complexes starting from the elemental, solid metals and neutral weakly coordinating ligands is established. This methodology reproduces as a benchmark the experimentally known redox potentials of reagents with excellent accuracy and is applied to a broad range of transition metals, weakly coordinating ligands, and solvents. The resulting redox scale follows chemically intuitive trends and identifies promising synthetic targets, while considering key influences on the potentials, such as metal ionization and sublimation energies, solvation energies, and coordinative strength of the ligand. This methodology provides a practical guide for selecting suitable deelectronators and assessing the feasibility of oxidative syntheses before experimental work is undertaken.