A trans-Hyponitrite Intermediate in the Reductive Coupling and Deoxygenation of Nitric Oxide by a Tricopper-Lewis Acid Complex

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 (N2O22-), 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 mu-O-bimetallic (Y,Cu) cores, a previously unreported coordination mode. Reaction of the hyponitrite species with Brousted 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 hi a subsequent step for N2O reduction to N-2, for an overall (partial) conversion of NO to N-2. The combination of Lewis acid, and multiple redox active metals facilitates this four electron conversion via an isolable hyponitrite intermediate.