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Contributing to the shift of this paradigm, we present here the discovery of a new and distinct heavy\u2010atom QMT reaction. Triplet syn\u20102\u2010formyl\u20103\u2010fluorophenylnitrene, generated in argon matrices by UV\u2010irradiation of an azide precursor, was found to spontaneously cyclize to singlet 4\u2010fluoro\u20102,1\u2010benzisoxazole. Monitoring the transformation by IR spectroscopy, temperature\u2010independent rate constants (<jats:italic>k<\/jats:italic>\u22481.4\u00d710<jats:sup>\u22123<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup>; half\u2010life of \u22488\u2005min) were measured from 10 to 20\u2005K. Computational estimated rate constants are in fair agreement with experimental values, providing evidence for a mechanism involving heavy\u2010atom QMT through crossing triplet to singlet potential energy surfaces. Moreover, the heavy\u2010atom QMT takes place with considerable displacement of the oxygen atom, which establishes a new limit for the heavier atom involved in a QMT reaction in cryogenic matrices.<\/jats:p>","DOI":"10.1002\/ange.202006640","type":"journal-article","created":{"date-parts":[[2020,6,18]],"date-time":"2020-06-18T05:25:40Z","timestamp":1592457940000},"page":"17775-17780","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Heavy\u2010Atom Tunneling Through Crossing Potential Energy Surfaces: Cyclization of a Triplet 2\u2010Formylarylnitrene to a Singlet 2,1\u2010Benzisoxazole"],"prefix":"10.1002","volume":"132","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8511-1230","authenticated-orcid":false,"given":"Cl\u00e1udio M.","family":"Nunes","sequence":"first","affiliation":[{"name":"University of Coimbra CQC Department of Chemistry  3004-535 Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2312-990X","authenticated-orcid":false,"given":"Lu\u00eds P.","family":"Viegas","sequence":"additional","affiliation":[{"name":"University of Coimbra CQC Department of Chemistry  3004-535 Coimbra Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8204-2770","authenticated-orcid":false,"given":"Samuel A.","family":"Wood","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Wisconsin-Madison  Madison WI 53706-1322 USA"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7845-9415","authenticated-orcid":false,"given":"Jos\u00e9 P. 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