title: A trans-Hyponitrite Intermediate in the Reductive Coupling and Deoxygenation of Nitric Oxide by a Tricopper-Lewis Acid Complex.
abstract: The reduction of nitric oxide (NO) to nitrous oxide (N2O) is a process relevant to biological chemistry as well as to the abatement of certain environmental pollutants. One of the proposed key intermediates in NO reduction is hyponitrite (N2O2(2-)), the product of reductive coupling of two NO molecules. We report the reductive coupling of NO by an yttrium-tricopper complex generating a trans-hyponitrite moiety supported by two μ-O-bimetallic (Y,Cu) cores, a previously unreported coordination mode. Reaction of the hyponitrite species with Brønsted acids leads to the generation of N2O, demonstrating the viability of the hyponitrite complex as an intermediate in NO reduction to N2O. The additional reducing equivalents stored in each tricopper unit are employed in a subsequent step for N2O reduction to N2, for an overall (partial) conversion of NO to N2. The combination of Lewis acid and multiple redox active metals facilitates this four electron conversion via an isolable hyponitrite intermediate.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, MC 127-72, Pasadena, California 91125, United States.
authors.forename: Davide
authors.initials: D
authors.lastname: Lionetti
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, MC 127-72, Pasadena, California 91125, United States.
authors.forename: Graham
authors.initials: G
authors.lastname: de Ruiter
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology , 1200 East California Boulevard, MC 127-72, Pasadena, California 91125, United States.
authors.forename: Theodor
authors.initials: T
authors.lastname: Agapie
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D058116:Lewis Acids / Q000737:chemistry*; D015394:Molecular Structure; D009569:Nitric Oxide / Q000737:chemistry*; D009573:Nitrites / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D009609:Nitrous Oxide / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D056831:Coordination Complexes; D058116:Lewis Acids; D009573:Nitrites; C025117:hyponitrite; D009569:Nitric Oxide; D003300:Copper; D009609:Nitrous Oxide; D009584:Nitrogen