A Redox‐Active Tetrazine‐Based Pincer Ligand for the Reduction of N‐Oxyanions Using a Redox‐Inert Metal

Beagan, Daniel M.; Maciulis, Nicholas A.; Pink, Maren; Carta, Veronica; Huerfano, I. J.; Chen, Chun‐Hsing; Caulton, Kenneth G.

doi:10.1002/chem.202101302

Title: A Redox‐Active Tetrazine‐Based Pincer Ligand for the Reduction of N‐Oxyanions Using a Redox‐Inert Metal

Journal Article · 02 July 2021 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.202101302 · OSTI ID:1805050

Beagan, Daniel M. ^[1]; Maciulis, Nicholas A. ^[1]; Pink, Maren ^[1]; Carta, Veronica ^[1]; Huerfano, I. J. ^[1]; Chen, Chun‐Hsing ^[1];

^[1]

Department of Chemistry Indiana University 47405 Bloomington Indiana USA

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)ZnX ₂ for X=Cl, NO ₃ and NO ₂ , 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 H ₄ btzp, containing two dihydrotetrazine reductants is described as is the synthesis and characterization of (H ₄ btzp)ZnX ₂ for X=Cl and NO ₃ , both of which show considerable hydrogen bonding potential of the dihydrotetrazine ring NH groups. The (H ₄ btzp)ZnCl ₂ complex does not bind zinc in the pincer pocket, but instead H ₄ btzp becomes a bridge between neighboring atoms through tetrazine nitrogen atoms, forming a polymeric chain. The reaction of AgNO ₂ with (H ₄ btzp)ZnCl ₂ is shown to proceed with fast nitrite deoxygenation, yielding water and free NO. Half of the H ₄ btzp reducing equivalents form Ag ⁰ and thus the chloride ligand remains coordinated to the zinc metal center to yield (btzp)ZnCl ₂ . To compare with AgNO ₂ , experiments of (H ₄ btzp)ZnCl ₂ with NaNO ₂ result in salt metathesis between chloride and nitrite, highlighting the importance of a redox‐active cation in the reduction of nitrite to NO.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1805050

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 45 Vol. 27; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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