Copper(I) Complex Mediated Nitric Oxide Reductive Coupling: Ligand Hydrogen Bonding Derived Proton Transfer Promotes N2O(g) Release

A cuprous chelate bearing a secondary sphere hydrogen bonding functionality, [(PV-tmpa)Cu-1](+), transforms (NO(g))-N-center dot to N2O(g) in high-yields in methanol. Ligand derived proton transfer facilitates N-O bond cleavage of a putative hyponitrite intermediate releasing N2O(g), underscoring the crucial balance between Hbonding capabilities and acidities in (bio)chemical (NO(g))-N-center dot coupling systems.