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Two product ions, NiAl<jats:sub>2<\/jats:sub>O<jats:sub>4<\/jats:sub>H<jats:sup>+<\/jats:sup> and NiAl<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>H<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup>, are identified in the mass spectra. The DFT calculations predict that the global minimum\u2010energy isomer of NiAl<jats:sub>2<\/jats:sub>O<jats:sub>4<\/jats:sub><jats:sup>+<\/jats:sup> contains Ni in the +II oxidation state and features a terminal Al\u2212O<jats:sup>.\u2212<\/jats:sup> oxygen radical site. They show that methane can react along two competing pathways leading to formation of either a methyl radical (CH<jats:sub>3<\/jats:sub>\u22c5) or formaldehyde (CH<jats:sub>2<\/jats:sub>O). Both reactions are initiated by hydrogen atom transfer from methane to the terminal O<jats:sup>.\u2212<\/jats:sup> site, followed by either CH<jats:sub>3<\/jats:sub>\u22c5 loss or CH<jats:sub>3<\/jats:sub>\u22c5 migration to an O<jats:sup>2\u2212<\/jats:sup> site next to the Ni<jats:sup>2+<\/jats:sup> center. The CH<jats:sub>3<\/jats:sub>\u22c5 attaches as CH<jats:sub>3<\/jats:sub><jats:sup>+<\/jats:sup> to O<jats:sup>2\u2212<\/jats:sup> and its unpaired electron is transferred to the Ni\u2010center reducing it to Ni<jats:sup>+<\/jats:sup>. The proposed mechanism is experimentally confirmed by vibrational spectroscopy of the reactant and two different product ions.<\/jats:p>","DOI":"10.1002\/anie.202202297","type":"journal-article","created":{"date-parts":[[2022,4,23]],"date-time":"2022-04-23T09:39:04Z","timestamp":1650706744000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["Gas\u2010Phase Mechanism of O<sup>.\u2212<\/sup>\/Ni<sup>2+<\/sup>\u2010Mediated Methane Conversion to Formaldehyde"],"prefix":"10.1002","volume":"61","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1877-1922","authenticated-orcid":false,"given":"Ya\u2010Ke","family":"Li","sequence":"first","affiliation":[{"name":"Wilhelm-Ostwald Institut f\u00fcr Physikalische und Theoretische Chemie Universit\u00e4t Leipzig  Linn\u00e9str. 2 04103 Leipzig Germany"},{"name":"Fritz-Haber-Institut der Max-Planck-Gesellschaft  Faradayweg 4\u20136 14195 Berlin Germany"},{"name":"Present 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