title: Can one oxidize an atom by reducing the molecule that contains it?
abstract: Negative values for the condensed Fukui function are identified as the key to designing molecules in which reduction of the molecule is associated with oxidation of one of the atomic centers, or vice versa. Sufficient conditions for negative condensed Fukui functions are derived, and metal complexes are identified as likely candidates for this exotic redox chemistry. Based on our theoretical understanding of where negative values of the Fukui function occur [P. W. Ayers, R. C. Morrison and R. K. Roy. J. Chem. Phys., 2002, 116, 8731], molecular-orbital diagrams for molecules where molecular oxidation is coupled to atomic reduction (or vice versa) are sketched. Whether one could design a metal complex with these properties is an open question but, if one could, then that compound would have fascinating redox chemistry and interesting magnetic properties. Candidate molecules for this property include metal complexes with small metal-to-ligand and/or ligand-to-metal charge transfer excitation energies.
authors.affiliation: Department of Chemistry, McMaster University, Hamilton, Ontario, Canada L8S 4M1.
authors.forename: Paul W
authors.initials: PW
authors.lastname: Ayers
mesh_terms: D003198:Computer Simulation; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D008670:Metals; D010100:Oxygen