The rate of CO2 increase and the supposed catastrophic consequences this is producing to our planet, thus it is obvious that our society has an urgent need for carbon-neutral renewable energy source. Otherwise, we must search for a way to fixate the CO2. And here we metal catalysts are a basic tool, however DFT calculations suggest monomeric catalysts are not enough. A dual metal system could be the solution? On the other hand a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes is presented (see Figure 1), using both experimental and computational methods. The dissociation of [{Au(NHC)}2(µ-OH)][BF4] is essential to enter the catalytic cycle; this step is favored in the presence of bulky, non-coordinating counterions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but as a co-catalyst, lowering the energy barriers for several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an ‘off-cycle’ rather than an ‘in-cycle’ intermediate. .References S. V. C. Vummaleti, S. P. Nolan, L. Cavallo, G. Talarico, A. Poater, Eur. J. Inorg. Chem. 2015, 4653-4657. V. D'Elia, H. Dong, A. Rossini, C. Widdifield, S. V. C. Vummaleti, Y. Minenkov, A. Poater, E. Abou-Hamad, J. Pelletier, L. Cavallo, L. Emsley, J. M. Basset, J. Am. Chem. Soc. 2015, 137, 7728-7739. V. D’ Elia, A. A. Ghani, A. Monassier, J. Sofack-Kreutzer, J. D. A. Pelletier, M. Drees, S. V. C. Vummaleti, A. Poater, L. Cavallo, M. Cokoja, J.-M. Basset, F. E. Kühn, Chem. Eur. J. 2014, 20, 11870-11882. Y. Oonishi, A. Gómez-Suárez, A. R. Martin, S. P. Nolan, Angew. Chem. Int. Ed. 2013, 52, 9767-9771. A. Gómez-Suárez, Y. Oonishi, A. R. Martin, S. V. C. Vummaleti, D. J. Nelson, D. B. Cordes, A. M. Z. Slawin, L. Cavallo, S. P. Nolan, A. Poater, Chem. Eur. J. 2016, accepted.

On the mechanism of the dual metal catalysis

251st National Meeting (2016)

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