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The results were reconciled to pertinent theories of electron transfer. \u03b1,\u03b2 \u2010Epoxyketones undergo dissociative electron\u2010transfer reactions with C\u2212O bond cleavage, via both stepwise and concerted mechanisms, depending on their structure. For aliphatic ketones, the preferred mechanism of reduction is consistent with the \u201csticky\u201d concerted model for dissociative electron transfer. Bond cleavage occurs simultaneously with electron transfer, and there is a residual, electrostatic interaction in the ring\u2010opened (distonic) radical anion. In contrast, for aromatic ketones, because the ring\u2010closed radical anions are resonance\u2010stabilized and exist at energy minima, a stepwise mechanism operates (electron transfer and bond cleavage occur in discrete steps). The rate constants for ring opening are on the order of 10<jats:sup>8<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup>, and not significantly affected by substituents on the 3\u2010membered ring (consistent with C\u2212O bond cleavage). These results and conclusions were fully supported and augmented by molecular orbital calculations.<\/jats:p>","DOI":"10.1002\/cplu.202000305","type":"journal-article","created":{"date-parts":[[2020,11,3]],"date-time":"2020-11-03T07:03:22Z","timestamp":1604387002000},"page":"2387-2396","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Interplay between Structure and Mechanism in Reductive Dissociative Electron Transfers to \u03b1,\u03b2 \u2010Epoxyketones"],"prefix":"10.1002","volume":"85","author":[{"given":"Jared N.","family":"Spencer","sequence":"first","affiliation":[{"name":"Department of Natural Sciences Montreat College  Montreat NC 28757 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Michelle L.","family":"Grimm","sequence":"additional","affiliation":[{"name":"Department of Chemistry Virginia Tech  Blacksburg VA 24060 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7349-5460","authenticated-orcid":false,"given":"James M.","family":"Tanko","sequence":"additional","affiliation":[{"name":"Department of Chemistry Virginia Tech  Blacksburg VA 24060 USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2020,11,3]]},"reference":[{"key":"e_1_2_6_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020617)41:12<2024::AID-ANIE2024>3.0.CO;2-O"},{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020617)114:12<2126::AID-ANGE2126>3.0.CO;2-6"},{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.2174\/1385272053369385"},{"key":"e_1_2_6_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201603993"},{"key":"e_1_2_6_4_1","unstructured":"\u00a0"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300583"},{"key":"e_1_2_6_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200300583"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/00404-0399(50)0975I-"},{"key":"e_1_2_6_7_2","doi-asserted-by":"crossref","unstructured":"A. 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