6. Computational study of ethene hydroarylation at [Ir(κ²-OAc)(PMe₃)Cp]⁺
   Davies, D. L.; Macgregor, S. A.; Poblador-Bahamonde, A. I.
   Dalton Trans. 2010, 39, 10520-10527

Density functional theory calculations have been employed to model ethene hydroarylation using an [Ir(κ²-OAc)(PMe₃)Cp]⁺ catalyst, 1. The reaction proceeds via: (i) an acetate-assisted C–H activation of benzene via an AMLA-6 transition state; (ii) rate-limiting insertion of ethene into the Ir–Ph bond; and (iii) protonolysis of the β-phenylethyl species by HOAc. A range of competing processes are assessed, the most important of which are the C–H activation of ethene at 1 and trapping of the β-phenylethyl intermediate with ethene. The former process gives rise to Ir–vinyl species which can then access further ethene insertion to give stable allyl by-products. A comparison with other ethene hydroarylation catalysts reported in the literature is presented.

DOI : 10.1039/c0dt00409j 

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