A cuprous chelate bearing a secondary sphere hydrogen bonding functionality, [(PV-tmpa)CuI]+, transforms •NO(g) 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 H-bonding capabilities and acidities in (bio)chemical •NO(g) coupling systems.