Inverted ligand fields present when frontier molecular orbitals are dominated by ligand character, leading to substantially more electron-rich metal centers than formalism implies. A key consequence is electron deficiency in ligands that renders them competent for reactivity including atom transfer and C–C bond formation. Evidence for ligand field inversion and the large rift between formalism and physicality will be presented including core spectroscopy and high resolution electron density analysis. Further support comes from electronic structure calculations including breathing orbital valence bond calculations. Case studies will be discussed including amination by formally high-valent Cu complexes, oxidation by Cu–aminoxyl adducts, and C–C bond formation involving formally Ni(II/IV) and Cu(I/III) couples.

Highly covalent to inverted ligand fields: Priming ligands for atom transfer and C–C bond formation

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