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This reduction is also significant in the global N cycle. Our previous experimental work showed that Fe and Co porphyrin NO complexes can couple with external NO to form N<jats:sub>2<\/jats:sub>O when activated by the Lewis acid BF<jats:sub>3<\/jats:sub>. A key difference from conventional two\u2010electron enzymatic reaction is that one electron is sufficient. However, a complete understanding of the entire reaction pathways and the more favorable reactivity for Fe remains unknown. Here, we present a quantum chemical study to provide such information. Our results confirmed Fe's higher experimental reactivity, showing advantages in all steps of the reaction pathway: easier metal oxidation for NO reduction and N\u2212O cleavage as well as a larger size to expedite the N\/O coordination mode transition. The Co system, with a similar product energy as the enzyme, shows potential for further development in catalytic NO coupling. This work also offers the first evidence that this new one\u2010electron NO reduction is both kinetically competitive and thermodynamically more favorable than the native pathway, supporting future initiatives in optimizing NO reduction agents in biology, environment, and industry.<\/jats:p>","DOI":"10.1002\/chem.202403677","type":"journal-article","created":{"date-parts":[[2024,10,31]],"date-time":"2024-10-31T11:39:50Z","timestamp":1730374790000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["One\u2010Electron NO to N<sub>2<\/sub>O Pathways via Heme Models and Lewis Acid: Metal Effects and Differences from the Enzymatic Reaction"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9170-9829","authenticated-orcid":false,"given":"Jia\u2010Min","family":"Chu","sequence":"first","affiliation":[{"name":"Department of Chemistry and Chemical Biology Stevens Institute of Technology  1 Castle Point Terrace Hoboken NJ 07030 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3212-7949","authenticated-orcid":false,"given":"Rahul L.","family":"Khade","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Stevens Institute of Technology  1 Castle Point Terrace Hoboken NJ 07030 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Vy","family":"Nguyen","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Stevens Institute of Technology  1 Castle Point Terrace Hoboken NJ 07030 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9400-0113","authenticated-orcid":false,"given":"George B.","family":"Richter\u2010Addo","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry University of Oklahoma  Norman OK 73019 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7207-6416","authenticated-orcid":false,"given":"Yong","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Stevens Institute of Technology  1 Castle Point Terrace Hoboken NJ 07030 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,11,19]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"\u00a0"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1361684"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr950056p"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1093891"},{"key":"e_1_2_8_5_2","unstructured":"L. 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