{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,18]],"date-time":"2026-03-18T15:28:11Z","timestamp":1773847691965,"version":"3.50.1"},"reference-count":106,"publisher":"Wiley","issue":"14","license":[{"start":{"date-parts":[[2019,2,21]],"date-time":"2019-02-21T00:00:00Z","timestamp":1550707200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["EXC\/314-1"],"award-info":[{"award-number":["EXC\/314-1"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2019,3,7]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Thermal gas\u2010phase reactions of the ruthenium\u2010oxide clusters [RuO<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>]<jats:sup>+<\/jats:sup> (<jats:italic>x=<\/jats:italic>1\u20133) with methane and dihydrogen have been explored by using FT\u2010ICR mass spectrometry complemented by high\u2010level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO]<jats:sup>+<\/jats:sup>\/CH<jats:sub>4<\/jats:sub> couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> brings about the generations of [Ru,O,C,H<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup>\/H<jats:sub>2<\/jats:sub>O, [Ru,O,C]<jats:sup>+<\/jats:sup>\/H<jats:sub>2<\/jats:sub>\/H<jats:sub>2<\/jats:sub>O, and [Ru,O,H<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup>\/CH<jats:sub>2<\/jats:sub>O, whereas [RuO<jats:sub>3<\/jats:sub>]<jats:sup>+<\/jats:sup> exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H<jats:sub>2<\/jats:sub>). Regarding the reactions with H<jats:sub>2<\/jats:sub>, as compared to CH<jats:sub>4<\/jats:sub>, both [RuO]<jats:sup>+<\/jats:sup> and [RuO<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> react similarly inefficiently with oxygen\u2010atom transfer being the main reaction channel; in contrast, [RuO<jats:sub>3<\/jats:sub>]<jats:sup>+<\/jats:sup> is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back\u2010bonding orbital interactions between the cluster ions and dihydrogen control the H\u2212H bond activation. Furthermore, the reactivity patterns of [RuO<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>]<jats:sup>+<\/jats:sup> (<jats:italic>x=<\/jats:italic>1\u20133) with CH<jats:sub>4<\/jats:sub> and H<jats:sub>2<\/jats:sub> have been compared with the previously reported results of Group\u20058 analogues [OsO<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>]<jats:sup>+<\/jats:sup>\/CH<jats:sub>4<\/jats:sub>\/H<jats:sub>2<\/jats:sub> (<jats:italic>x=<\/jats:italic>1\u20133) and the [FeO]<jats:sup>+<\/jats:sup>\/H<jats:sub>2<\/jats:sub> system. The electronic origins for their distinctly different reaction behaviors have been addressed.<\/jats:p>","DOI":"10.1002\/chem.201806187","type":"journal-article","created":{"date-parts":[[2019,1,25]],"date-time":"2019-01-25T07:12:47Z","timestamp":1548400367000},"page":"3550-3559","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Thermal Activation of CH<sub>4<\/sub> and H<sub>2<\/sub> as Mediated by the Ruthenium Oxide Cluster Ions [RuO<sub><i>x<\/i><\/sub>]<sup>+<\/sup> (<i>x=<\/i>1\u20133): On the Influence of Oxidation States"],"prefix":"10.1002","volume":"25","author":[{"given":"Xiaoyan","family":"Sun","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Chemie Technische Universit\u00e4t Berlin  Stra\u00dfe des 17. 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