{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,11]],"date-time":"2026-02-11T12:56:27Z","timestamp":1770814587477,"version":"3.50.1"},"reference-count":32,"publisher":"Wiley","issue":"25","license":[{"start":{"date-parts":[[2015,5,12]],"date-time":"2015-05-12T00:00:00Z","timestamp":1431388800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2015,6,15]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Biological [Fe\u2010S] clusters are increasingly recognized to undergo proton\u2010coupled electron transfer (PCET), but the site of protonation, mechanism, and role for PCET remains largely unknown. Here we explore this reactivity with synthetic model clusters. Protonation of the arylthiolate\u2010ligated [4Fe\u20104S] cluster [Fe<jats:sub>4<\/jats:sub>S<jats:sub>4<\/jats:sub>(SAr)<jats:sub>4<\/jats:sub>]<jats:sup>2\u2212<\/jats:sup> (<jats:bold>1<\/jats:bold>, SAr=S\u20102,4\u20106\u2010(<jats:italic>i<\/jats:italic>Pr)<jats:sub>3<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>2<\/jats:sub>) leads to thiol dissociation, reversibly forming [Fe<jats:sub>4<\/jats:sub>S<jats:sub>4<\/jats:sub>(SAr)<jats:sub>3<\/jats:sub>L]<jats:sup>1\u2212<\/jats:sup> (<jats:bold>2<\/jats:bold>) and ArSH (L=solvent, and\/or conjugate base). Solutions of <jats:bold>2<\/jats:bold>+ArSH react with the nitroxyl radical TEMPO to give [Fe<jats:sub>4<\/jats:sub>S<jats:sub>4<\/jats:sub>(SAr)<jats:sub>4<\/jats:sub>]<jats:sup>1\u2212<\/jats:sup> (<jats:bold>1<jats:sub>ox<\/jats:sub><\/jats:bold>) and TEMPOH. This reaction involves PCET coupled to thiolate association and may proceed via the unobserved protonated cluster [Fe<jats:sub>4<\/jats:sub>S<jats:sub>4<\/jats:sub>(SAr)<jats:sub>3<\/jats:sub>(HSAr)]<jats:sup>1\u2212<\/jats:sup> (<jats:bold>1\u2010H<\/jats:bold>). Similar reactions with this and related clusters proceed comparably. An understanding of the PCET thermochemistry of this cluster system has been developed, encompassing three different redox levels and two protonation states.<\/jats:p>","DOI":"10.1002\/chem.201500152","type":"journal-article","created":{"date-parts":[[2015,5,12]],"date-time":"2015-05-12T11:44:36Z","timestamp":1431431076000},"page":"9256-9260","source":"Crossref","is-referenced-by-count":19,"title":["Protonation and Proton\u2010Coupled Electron Transfer at S\u2010Ligated [4Fe\u20104S] Clusters"],"prefix":"10.1002","volume":"21","author":[{"given":"Caroline T.","family":"Saouma","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Wesley D.","family":"Morris","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Julia W.","family":"Darcy","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"James M.","family":"Mayer","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2015,5,12]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi0350957"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi9016445"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi035021v"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja961465l"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi980048d"},{"key":"e_1_2_6_7_2","volume-title":"Principles of Bioinorganic Chemistry","author":"Lippard S. J.","year":"1994"},{"key":"e_1_2_6_8_2","unstructured":"\u00a0"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja205304t"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar300267m"},{"key":"e_1_2_6_11_2","unstructured":"\u00a0"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0sc00545b"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/a803223h"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00388a085"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00148a019"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0162-0134(00)80019-7"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39870000674"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja311310k"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2004.12.021"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00299a066"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020615"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00485a014"},{"key":"e_1_2_6_23_2","volume-title":"Acid\u2010Base Dissociation Constants in Dipolar Aprotic Solvents","author":"Izutsu K.","year":"1990"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00419a010"},{"key":"e_1_2_6_25_2","unstructured":"\u00a0"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4DT01687D"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1039\/c4cc00922c"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00016a022"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100085k"},{"key":"e_1_2_6_30_2","unstructured":"For the purposes of this Figure we assume L is a molecule of solvent. Under the reaction conditions of millimolar reagents the2+ArSH\u21cc1\u2010H+L equilibrium lies strongly to the left. The reason that the minimum energy of the1\u2010H+L state is still placed lower than2+ArSH in Figure\u20051 (top) is that the diagram shows the energies at standard state (1\u2009Mconcentrations). This equilibrium involves two molecules going to one (the solvent L not being included in the equilibrium expression) so the2+ArSH side is more favored at lower concentrations. This leads to the minimum value of \u0394G\u00b0l.e.of \u22121.9\u2005kcal\u2009mol\u22121based on the observation thatKl.e.\u226a1."},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja3019324"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi9626665"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201500152","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201500152","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T18:20:53Z","timestamp":1760293253000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201500152"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2015,5,12]]},"references-count":32,"journal-issue":{"issue":"25","published-print":{"date-parts":[[2015,6,15]]}},"alternative-id":["10.1002\/chem.201500152"],"URL":"https:\/\/doi.org\/10.1002\/chem.201500152","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2015,5,12]]}}}