DFT and Experimental Studies on the PtX2/X–-Catalyzed Olefin Hydroamination: Effect of Halogen, Amine Basicity, and Olefin on Activity, Regioselectivity, and Catalyst Deactivation

A DFT/B3LYP study with inclusion of solvent and temperature effects has probed the olefin activation mechanism for the intermolecular hydroamination of ethylene and 1-hexene by aniline derivatives catalyzed by the PtX2/X– system on the basis of a variety of experimental results, including new experiments on catalyst deactivation. For ethylene and aniline, the calculated ΔG‡cycle between the resting state [PtX3(C2H4)]−, 1X, and the TOF-determining transition state of the C–H reductive elimination from [PtX3(H)(CH2CH2NHPh)]−, TS2X, is slightly smaller for X = Br than for Cl or I. The ΔG‡cycle decreases as the aniline basicity decreases. For the slightly less efficient hydroamination of 1-hexene, ΔG‡cycle is greater than that for the hydroamination of ethylene, with a preference for the Markovnikov addition, in agreement with experiment and with essentially equivalent ΔG‡cycle values for the Br and I systems. In general, the results of the calculations are in agreement with the experimental observation. A cl...

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