Lewis acid-assisted reduction of nitrite to nitric and nitrous oxides via the elusive nitrite radical dianion

Hosseininasab, Valiallah; DiMucci, Ida M.; Ghosh, Pokhraj; Bertke, Jeffery A.; Chandrasekharan, Siddarth; Titus, Charles J.; Nordlund, Dennis; Freed, Jack H.; Lancaster, Kyle M.; Warren, Timothy H.

doi:10.1038/s41557-022-01025-9

Lewis acid-assisted reduction of nitrite to nitric and nitrous oxides via the elusive nitrite radical dianion

Journal Article · Mon Sep 05 00:00:00 EDT 2022 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-022-01025-9· OSTI ID:1988064

Hosseininasab, Valiallah ^[1]; DiMucci, Ida M. ^[2]; Ghosh, Pokhraj ^[3]; Bertke, Jeffery A. ^[4]; ^[2]; ^[5]; ^[6]; ^[2]; ^[2]; ^[3]

Georgetown University, Washington, DC (United States); SLAC
Cornell University, Ithaca, NY (United States)
Georgetown University, Washington, DC (United States); Michigan State University, East Lansing, MI (United States)
Georgetown University, Washington, DC (United States)
Stanford University, CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Reduction of nitrite anions (NO₂^-) to nitric oxide (NO), nitrous oxide (N₂O) and ultimately dinitrogen (N₂) takes place in a variety of environments, including in the soil as part of the biogeochemical nitrogen cycle and in acidified nuclear waste. Nitrite reduction typically takes place within the coordination sphere of a redox-active transition metal. In this report we show that Lewis acid coordination can substantially modify the reduction potential of this polyoxoanion to allow for its reduction under non-aqueous conditions (-0.74 V versus NHE). Detailed characterization confirms the formation of the borane-capped radical nitrite dianion (NO₂^2-), which features a N(II) oxidation state. Protonation of the nitrite dianion results in the facile loss of nitric oxide (NO), whereas its reaction with NO results in disproportionation to nitrous oxide (N₂O) and nitrite (NO₂^-). This system connects three redox levels in the global nitrogen cycle and provides fundamental insights into the conversion of NO₂^- to NO.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1988064

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 11 Vol. 14; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Lewis acid-assisted reduction of nitrite to nitric and nitrous oxides via the elusive nitrite radical dianion

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