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Pure main\u2010group compounds capable of this are rare and have emerged in recent decades. These systems rely on synergistic donor\u2010acceptor interactions with H\n                    <jats:sub>2<\/jats:sub>\n                    \u2019s antibonding \u03c3* and bonding \u03c3 orbital. An alternative (hydrocarbon) radical\u2010mediated activation is problematic because the H\u2212H bond is stronger (104.2\u2005kcal\u2009mol\n                    <jats:sup>\u22121<\/jats:sup>\n                    ) than most C\u2212H bonds. Here, we explore using the phenyl radical to tackle this, forming benzene with a C\u2212H bond energy (112.9\u2005kcal\u2009mol\n                    <jats:sup>\u22121<\/jats:sup>\n                    ) that provides a thermodynamic driving force. We mainly observe a benzene\u2010HI complex upon photolysis of iodobenzene in an H\n                    <jats:sub>2<\/jats:sub>\n                    \u2010doped neon matrix at 4.4\u2005K despite a barrier of 7.6\u2005kcal\u2009mol\n                    <jats:sup>\u22121<\/jats:sup>\n                    , while phenyl radical forms in case of the heavier D\n                    <jats:sub>2<\/jats:sub>\n                    isotopologue. When D\n                    <jats:sub>2<\/jats:sub>\n                    molecules are allowed to diffuse, mono\u2010deuterated benzene accumulates within hours. Computations using path integral\u2010based instanton theory highlight that primarily the transferred hydrogen atom is moving during the reaction which greatly increases the tunneling probability. In excellent agreement with the experimental results, we predict significant tunneling rate constants for both isotopologues, H\n                    <jats:sub>2<\/jats:sub>\n                    and D\n                    <jats:sub>2<\/jats:sub>\n                    , featuring a strong kinetic isotope effect of up to four orders of magnitude at the lowest temperatures.\n                  <\/jats:p>","DOI":"10.1002\/anie.202414573","type":"journal-article","created":{"date-parts":[[2024,9,30]],"date-time":"2024-09-30T03:59:40Z","timestamp":1727668780000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Phenyl Radical Activates Molecular Hydrogen Through Protium and Deuterium Tunneling"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4146-308X","authenticated-orcid":false,"given":"Virinder","family":"Bhagat","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Eberhard Karls Universit\u00e4t T\u00fcbingen  Auf der Morgenstelle\u200518 72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1301-2612","authenticated-orcid":false,"given":"Jan","family":"Meisner","sequence":"additional","affiliation":[{"name":"Institute for Physical Chemistry Heinrich Heine University D\u00fcsseldorf  Universit\u00e4tsstra\u00dfe\u20051 40225 D\u00fcsseldorf Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1433-0292","authenticated-orcid":false,"given":"Jan Philipp","family":"Wagner","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Organische Chemie Eberhard Karls Universit\u00e4t T\u00fcbingen  Auf der Morgenstelle\u200518 72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,11,13]]},"reference":[{"key":"e_1_2_9_1_1","first-page":"1358","author":"Sabatier P.","year":"1897","journal-title":"C.\u2005R. 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