{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,20]],"date-time":"2026-10-20T09:18:22Z","timestamp":1792487902763,"version":"4.5.0"},"reference-count":31,"publisher":"Wiley","issue":"2","license":[{"start":{"date-parts":[[2019,11,14]],"date-time":"2019-11-14T00:00:00Z","timestamp":1573689600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000002","name":"National Institutes of Health","doi-asserted-by":"publisher","award":["R01 GM116820"],"award-info":[{"award-number":["R01 GM116820"]}],"id":[{"id":"10.13039\/100000002","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2020,1,7]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The model complex [Cu<jats:sub>4<\/jats:sub>(\u03bc<jats:sub>4<\/jats:sub>\u2010S)(dppa)<jats:sub>4<\/jats:sub>]<jats:sup>2+<\/jats:sup> (<jats:bold>1<\/jats:bold>, dppa=\u03bc<jats:sub>2<\/jats:sub>\u2010(Ph<jats:sub>2<\/jats:sub>P)<jats:sub>2<\/jats:sub>NH) has N<jats:sub>2<\/jats:sub>O reductase activity in methanol solvent, mediating 2\u2009H<jats:sup>+<\/jats:sup>\/2\u2009e<jats:sup>\u2212<\/jats:sup> reduction of N<jats:sub>2<\/jats:sub>O to N<jats:sub>2<\/jats:sub>+H<jats:sub>2<\/jats:sub>O in the presence of an exogenous electron donor (CoCp<jats:sub>2<\/jats:sub>). A stoichiometric product with two deprotonated dppa ligands was characterized, indicating a key role of second\u2010sphere N\u2212H residues as proton donors during N<jats:sub>2<\/jats:sub>O reduction. The activity of <jats:bold>1<\/jats:bold> towards N<jats:sub>2<\/jats:sub>O was suppressed in solvents that are unable to provide hydrogen bonding to the second\u2010sphere N\u2212H groups. Structural and computational data indicate that second\u2010sphere hydrogen bonding induces structural distortion of the [Cu<jats:sub>4<\/jats:sub>S] active site, accessing a strained geometry with enhanced reactivity due to localization of electron density along a dicopper edge site. The behavior of <jats:bold>1<\/jats:bold> mimics aspects of the Cu<jats:sub>Z<\/jats:sub> catalytic site of nitrous oxide reductase: activity in the 4Cu<jats:sup>I<\/jats:sup>:1S redox state, use of a second\u2010sphere proton donor, and reactivity dependence on both primary and secondary sphere effects.<\/jats:p>","DOI":"10.1002\/anie.201906327","type":"journal-article","created":{"date-parts":[[2019,10,29]],"date-time":"2019-10-29T13:21:02Z","timestamp":1572355262000},"page":"627-631","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":36,"title":["N<sub>2<\/sub>O Reductase Activity of a [Cu<sub>4<\/sub>S] Cluster in the 4Cu<sup>I<\/sup> Redox State Modulated by Hydrogen Bond Donors and Proton Relays in the Secondary Coordination Sphere"],"prefix":"10.1002","volume":"59","author":[{"given":"Chia\u2010Wei","family":"Hsu","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Illinois at Chicago  845 W. Taylor St. Chicago IL 60607 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Suresh C.","family":"Rathnayaka","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Illinois at Chicago  845 W. Taylor St. Chicago IL 60607 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shahidul M.","family":"Islam","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Illinois at Chicago  845 W. Taylor St. Chicago IL 60607 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Samantha N.","family":"MacMillan","sequence":"additional","affiliation":[{"name":"Department of Chemistry &amp; Chemical Biology Cornell University, Baker Laboratory  Ithaca NY 14853 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6923-5164","authenticated-orcid":false,"given":"Neal P.","family":"Mankad","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Illinois at Chicago  845 W. 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