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言語:
eng - English
日付:
2013-01-102013-02-122013-02-222013-03-06
出版の状態:
出版
ページ:
11
出版情報:
-
目次:
The heteronuclear oxo cluster [VPO<sub>4</sub>]<sup>•+</sup> is generated via electrospray-ionization (ESI) and investigated with respect to both its electronic structure as well as its gas-phase reactivity towards small hydrocarbons, thus permitting a comparison to the well-known vanadium-oxide cation [V<sub>2</sub>O<sub>4</sub>]<sup>•+</sup>. As described in previous studies, the latter oxide exhibits no reactivity towards small hydrocarbons, such as CH<sub>4</sub>, C<sub>2</sub>H<sub>6</sub>, C<sub>3</sub>H<sub>8</sub>, n-C<sub>4</sub>H<sub>10</sub>, and C<sub>2</sub>H<sub>4</sub>, while substitution of one vanadium by a phosphorous atom yields the reactive [VPO<sub>4</sub>]<sup>•+</sup> ion; the latter brings about oxidative dehydrogenation of saturated hydrocarbons, e.g. propane and butane, as well as oxygen-atom transfer to unsaturated hydrocarbons, e.g. ethene, at thermal conditions. Further, the gas-phase structure of [VPO<sub>4</sub>]<sup>•+</sup> is determined by IR photodissociation spectroscopy and compared to that of [V<sub>2</sub>O<sub>4</sub>]<sup>•+</sup>. DFT calculations help to elucidate the reaction mechanism. The results underline the crucial role of phosphorous in terms of C–H bond activation of hydrocarbons by mixed VPO-clusters.
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学位:
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