Modeling Reactivity of Nitrite and Nitrous Acid at a Phenolate Bridged Dizinc(II) Site: Insights into NO Signaling at Zinc.

Although nitrite-to-NO transformation at various transition metals including Fe and Cu are relatively well explored, examples of such a reaction at the redox-inactive zinc(II) site are limited. The present report aims to gain insights into the reactivity of nitrite anions, nitrous acid (HONO), and organonitrite (RONO) at a dizinc(II) site. A phenolate-bridged dizinc(II)-aqua complex [L Zn (OH )] (ClO ) (1 -Aq, where L =tridentate N,N,O-donor monoanionic ligand) is illustrated to react with BuONO to provide a metastable arene-nitrosonium charge-transfer complex 2 .