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The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H<jats:sub>2<\/jats:sub>SO<jats:sub>2<\/jats:sub><jats:sup>.+<\/jats:sup>, the radical cation of sulfoxylic acid. The mechanism of the double C\uf8ffH activation, in the absence of the single activation product HSO<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup>, is elucidated by kinetic studies and quantum chemical calculations. Under near single\u2010collision conditions the reaction occurs with rate constant <jats:italic>k<\/jats:italic>=1.0\u00d710<jats:sup>\u22129<\/jats:sup> (\u00b130\u2009%)\u2005cm<jats:sup>3<\/jats:sup>\u2009s<jats:sup>\u22121<\/jats:sup>\u2009molecule<jats:sup>\u22121<\/jats:sup>, efficiency=90\u2009%, kinetic isotope effect <jats:italic>k<\/jats:italic><jats:sub>H<\/jats:sub>\/<jats:italic>k<\/jats:italic><jats:sub>D<\/jats:sub>=1.1, and partial H\/D scrambling. The theoretical analysis shows that the interaction of SO<jats:sub>2<\/jats:sub><jats:sup>.+<\/jats:sup> with ethane through an oxygen atom directly leads to the C\uf8ffH activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C\uf8ffH activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H\/D scrambling. Key issues in the observed reactivity are electron\u2010transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal\u2010free electrophiles may contribute to the current understanding of the C\uf8ffH activation of ethane.<\/jats:p>","DOI":"10.1002\/chem.200903588","type":"journal-article","created":{"date-parts":[[2010,4,21]],"date-time":"2010-04-21T02:03:59Z","timestamp":1271815439000},"page":"6234-6242","source":"Crossref","is-referenced-by-count":34,"title":["Double C\uf8ffH Activation of Ethane by Metal\u2010Free SO<sub>2<\/sub><sup>.+<\/sup> Radical 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