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Abstract The reaction chemistry of the bis‐tetrazinyl pyridine ligand (btzp) towards nitrogen oxyanions coordinated to zinc is studied in order to explore the reduction of the NO_x⁻substrates with a redox‐active ligand in the absence of redox activity at the metal. Following syntheses and characterization of (btzp)ZnX₂for X=Cl, NO₃and NO₂, featuring O−Zn linkage of both nitrogen oxyanions, it is shown that a silylating agent selectively delivers silyl substituents to tetrazine nitrogens, without reductive deoxygenation of NO_x⁻¹. A new synthesis of the highly hydrogenated H₄btzp, containing two dihydrotetrazine reductants is described as is the synthesis and characterization of (H₄btzp)ZnX₂for X=Cl and NO₃, both of which show considerable hydrogen bonding potential of the dihydrotetrazine ring NH groups. The (H₄btzp)ZnCl₂complex does not bind zinc in the pincer pocket, but instead H₄btzp becomes a bridge between neighboring atoms through tetrazine nitrogen atoms, forming a polymeric chain. The reaction of AgNO₂with (H₄btzp)ZnCl₂is shown to proceed with fast nitrite deoxygenation, yielding water and free NO. Half of the H₄btzp reducing equivalents form Ag⁰and thus the chloride ligand remains coordinated to the zinc metal center to yield (btzp)ZnCl₂. To compare with AgNO₂, experiments of (H₄btzp)ZnCl₂with NaNO₂result in salt metathesis between chloride and nitrite, highlighting the importance of a redox‐active cation in the reduction of nitrite to NO.