Reactivity of Metal Carbene Clusters PtnCH2+ and PtMCH2+ (M = Cu, Ag, Au, Pt, Rh) Toward O2 and NH3: A Computational Study

  • Zexing Cao


DFT calculations at various levels have been used to elucidate the mechanistic details of dehydrogenation of methane by Pt cationic clusters and the reactivity of metal carbene clusters Pt4CH 2 + and PtMCH 2 + (M = Cu, Ag, Au, Pt, Rh) toward O2 and NH3. On the basis of theoretical analyses, the size dependence of reactivity and the cooperative effect of the bimetallic cluster in the dehydrogenation reactions of CH4 and NH3 have been discussed. Plausible mechanisms for the reactions of Pt4CH 2 + with O2 and PtMCH 2 + with NH3, leading to C–O and C–N bond couplings, respectively, have been proposed. The calculated results show good agreement with the experimental observations and provide a reasonable basis for understanding of the gas-phase chemistry of bare Pt-containing cationic clusters and their organometallic systems.


Potential Energy Surface Bond Activation Dehydrogenation Reaction Quartet State Bimetallic Cluster 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



Zexing Cao thanks his students and collaborators as cited in the references for their key contributions to this research. This work was supported by the National Science Foundation of China (20673087, 20733002, 20873105) and the Ministry of Science and Technology (2011CB808504).


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Authors and Affiliations

  1. 1.Department of Chemistry and State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical EngineeringXiamen UniversityXiamenChina

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