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For the MO<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold><jats:sup>+<\/jats:sup>\/CH<jats:sub>4<\/jats:sub> couples abstraction of a hydrogen atom to form MOH<jats:sup>+<\/jats:sup> and a methyl radical constitutes the sole channel. The nearly barrier\u2010free process, combined with a large exothermicity as revealed by density functional theory (DFT) calculations, suggests a fast and efficient reaction in agreement with the experiment. For the IMR of MO<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold><jats:sup>+<\/jats:sup> with ethene, two competitive channels exist: hydrogen\u2010atom abstraction (HAA) from and oxygen\u2010atom transfer (OAT) to the organic substrate. The HAA channel, yielding C<jats:sub>2<\/jats:sub>H<jats:sub>3<\/jats:sub><jats:bold><jats:sup>.<\/jats:sup><\/jats:bold> and MOH<jats:sup>+<\/jats:sup> predominates for the GeO<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold><jats:sup>+<\/jats:sup>\/ethene system, while for SnO<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold><jats:sup>+<\/jats:sup> and PbO<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold><jats:sup>+<\/jats:sup> the major reaction observed corresponds to the OAT producing M<jats:sup>+<\/jats:sup> and C<jats:sub>2<\/jats:sub>H<jats:sub>4<\/jats:sub>O. The DFT\u2010derived potential\u2010energy surfaces are consistent with the experimental findings. The behavior of the metal oxide cations towards ethene can be explained in terms of the bond dissociation energies (BDEs) of MO<jats:sup>+<\/jats:sup>\uf8ffH and M<jats:sup>+<\/jats:sup>\uf8ffO, which define the hydrogen\u2010atom affinity of MO<jats:sup>+<\/jats:sup> and the oxophilicity of M<jats:sup>+<\/jats:sup>, respectively. Since the differences among the BDEs(MO<jats:sup>+<\/jats:sup>\uf8ffH) are rather small and the hydrogen\u2010atom affinities of the three radical cations MO<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold><jats:sup>+<\/jats:sup> exceed the BDE(CH<jats:sub>3<\/jats:sub>\uf8ffH) and BDE(C<jats:sub>2<\/jats:sub>H<jats:sub>3<\/jats:sub>\uf8ffH), hydrogen\u2010atom abstraction is possible thermochemically. In contrast, the BDEs(M<jats:sup>+<\/jats:sup>\uf8ffO) vary quite substantially; consequently, the OAT channel becomes energetically less favorable for GeO<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold><jats:sup>+<\/jats:sup> which exhibits the highest oxophilicity among these three group 14 metal ions.<\/jats:p>","DOI":"10.1002\/chem.201101538","type":"journal-article","created":{"date-parts":[[2011,8,4]],"date-time":"2011-08-04T12:33:27Z","timestamp":1312461207000},"page":"9619-9625","source":"Crossref","is-referenced-by-count":48,"title":["Thermal Activation of Methane and Ethene by Bare MO<sup>.+<\/sup> (M=Ge, Sn, and Pb): A Combined Theoretical\/Experimental Study"],"prefix":"10.1002","volume":"17","author":[{"given":"Kai","family":"Chen","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zhe\u2010Chen","family":"Wang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Maria","family":"Schlangen","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yun\u2010Dong","family":"Wu","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xinhao","family":"Zhang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Helmut","family":"Schwarz","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2011,8,4]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19911030711"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199108201"},{"volume-title":"Heterogeneous Hydrocarbon Oxidation","year":"1996","key":"e_1_2_6_3_2"},{"volume-title":"Catalytic Selective Oxidation","year":"1993","key":"e_1_2_6_4_2"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900183p"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","first-page":"3","volume":"23","author":"Barton D. 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