期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 16, 期 13, 页码 4110-4119出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200902373
关键词
alkanes; C-H activation; density functional calculations; magnesium oxide; selectivity
资金
- Academy of Sciences of the Czech Republic [Z40550506]
- European Research Council [AdG226373]
- Grant Agency of the Academy of Sciences of the Czech Republic [KJB400550704]
- Grant Agency of the Czech Republic [203/08/1487]
- Ministry of Education of the Czech Republic [MSM0021620857, RP MSMT 14/63]
- German Research Foundation
The C-H bond activation of small alkanes by the gaseous MgO+center dot cation is probed by mass spectrometric means. In addition to H-atom abstraction from methane, the MgO+center dot cation reacts with ethane, propane, n- and isobutane through several pathways, which can all be assigned to the occurrence of initial C-H bond activations. Specifically, the formal C-C bond cleavages observed are assigned to C-H bond activation as the first step, followed by cleavage of a beta-C-C bond concomitant with release of the corresponding alkyl radical. Kinetic modeling of the observed product distributions reveals a high preference of MgO+center dot for the attack of primary C-H bonds. This feature represents a notable distinction of the main-group metal oxide MgO+center dot from various transition-metal oxide cations, which show a clear preference for the attack of secondary C-H bonds. The results of complementary theoretical calculations indicate that the C-H bond activation of larger alkanes by the MgO+center dot cation is subject to pronounced kinetic control.
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