The electronic structure of lanthanide materials and complexes is driven by the relative role of the metal valence orbitals in metal-ligand bonding and the effects of charge localization within ligand framework. The redox chemistry of f-element molecular complexes has emerged as a powerful process with which to interrogate the role of the metal valence f- and d- orbitals in metal-ligand bonding within a conserved ligand framework. A redox pair of tetrahomoleptic Ce(3+/4+) imidophosphorane complexes is presented. The trivalent imidophosphorane complex is the most reducing reported to date (&lt; -2.64 V vs. Fc/Fc+ (as determined by solution reactivity) and -2.99 V vs. Fc/Fc+ (as determined by DFT)) and is heavily dependent on inner sphere supporting cation. The redox chemistry of this imidophosphorane redox pair and related complexes is presented. The unique stabilization of the tetravalent state has been analyzed spectroscopically (UV/vis/NIR, EPR, L3-edge XAS) and theoretically to understand the dependence of the tetravalent oxidation state on covalent and ionic interactions between the metal and ligand.

Homoleptic imidophosphorane cerium complexes: Potent thermodynamic reductants and stabilization of tetravalent oxidation state

2019 Spring National Meeting

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