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dc.contributor.authorFei Xia
dc.contributor.authorKuo Zeng
dc.contributor.authorZexing Cao
dc.contributor.author曹泽星
dc.date.accessioned2011-11-21T01:12:40Z
dc.date.available2011-11-21T01:12:40Z
dc.date.issued2005-03
dc.identifier.citationOrganometallics, 2005, 24 (8): 1845–1851zh_CN
dc.identifier.issn0276-7333
dc.identifier.issnhttp://dx.doi.org/doi:10.1021/om0490942
dc.identifier.urihttps://dspace.xmu.edu.cn/handle/2288/11212
dc.description.abstractDehydrogenation and C-N coupling from PtMCH2+ (M = Pt, Au) and ammonia have been investigated by the density functional methodology. The structure and stability of intermediates and ionic products as well as detailed mechanisms for loss of H-2 and degradation of the metal core have been discussed. Calculations reveal that in the case of Pt2CH2+ only direct elimination of H-2 from the moiety of CH2 occurs in the adduct (NH3)Pt2CH2+, and the activation energy for the rate-determining step is about 30 kcal mol(-1). The overall reaction is exothermic by similar to 30 kcal mol(-1). The heterometallic carbene PtAuCH2+ exhibits reactivity different from Pt2CH2+. The dehydrogenation from C-H and NH3 activation can occur in competitive mechanisms, where the channel to loss of H-2 from the stepwise N-H and C-H activation is more favorable than the elimination of H-2 in methylene or in NH3 both thermodynamically and dynamically. The ionic product aminocarbene AuPtCHNH2+ reacts with NH3, giving rise to the loss of H-2 and AuH. Predicted relative energetics and barriers along suggested reaction paths are in reasonable agreement with experimental observations. Different reactivities of PtAuCH2+ and Pt2CH2+ in the gas-phase reactions with NH3 arise from distinct geometrical and electronic structures of their reactive precursors.zh_CN
dc.language.isoenzh_CN
dc.publisherAMER CHEMICAL SOCzh_CN
dc.titleDensity functional characterization of reactions of bimetallic carbenes PtMCH2+ (M = Pt, Au) with NH3 in the gas phasezh_CN
dc.typeArticlezh_CN


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