The reactions of methane with the gold complexes [Au(OH)]−, [Au(OCH3)4]−, [Au(O(CO)2O2]− and [Au(O2CH)2]+, [AuI(acac)], [AuIII(acac)2]+ (acac-acetylacetonato) were studied using the DFT/PBE method with the SBK basis set. High activation barriers were obtained for the electrophilic substitution in [Au(OH)]−, [Au(OCH3)4]−, [Au(O(CO)2O)2]-and [AuIII(acac)2]+ complexes, which excludes the possibility that these reactions might proceed under mild conditions. The reactions of the [Au(HCO2)2]+ and [AuI(acac)] complexes with methane have rather low energy barriers and proceed through the formation of an intermediate complex. The alternative mechanism of methane oxidation with a gold complex in the presence of oxygen is simulated.
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Prof. NE Kuz'menko is Professor of Physical Chemistry at the M.V. Lomonosov Moscow State University. He carried out his Diploma and PhD in the field of theoretical chemistry and molecular spectroscopy. He is currently Head of the Laboratory of Molecular Spectroscopy and Vice-Dean of the Chemistry Department of MSU.
Head of the Laboratory of Transition Metal Catalysis in the Institute of Problems of Physical Chemistry. The scope of his scientific interests is the theoretical study of activation of small molecules in the coordination sphere of transition metal complexes, i.e. C-H bond activation and nitrogen fixation.
DA Pichugina PhD works in Professors N.E. Kuz'menko's and A.F. Shestakov's group where they study the interaction and reactions of small molecules with gold nanoclusters and gold compounds using quantum chemistry methods.
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Pichugina, D., Kuz'menko, N. & Shestakov, A. Gold complexes with. Gold Bull 40, 115–120 (2007). https://doi.org/10.1007/BF03215567
- Gold complexes
- methane activation
- quantum chemical methods