Arene C–H bond activation and methane formation by a methylplatinum(ii) complex: experimental and theoretical elucidation of the mechanism?

New Journal of Chemistry Pub Date: 2019-04-26 DOI: 10.1039/C9NJ01968E

Abstract

In a combined experimental/computational investigation, the behavior of neutral complex [PtMe2(DMSO)2], 1, has been explored in the cyclometalation reaction with HC^N ligands (HC^N = 2-(p-tolyl)pyridine (Htpy), 2-phenylpyridine (Hppy), 1-phenylpyrazole (Hppz) and benzo[h]quinoline (Hbhq)). The losses of DMSO from [PtMe2(DMSO)2], 1, activation of the Csp2–H bond of HC^N and then the liberation of methane result in the formation of a cyclometalated [PtMe(C^N)(DMSO)] complex. The experimental studies complemented by DFT calculations indicate that the reaction of 1 with HC^N proceeds via HC^N coordination through the N donor atom, intramolecular oxidative addition of the arene C–H bond, and final dissociation of methane from a platinum hydride complex. The kinetic parameters for the C–H activation process are also determined.

Graphical abstract: Arene C–H bond activation and methane formation by a methylplatinum(ii) complex: experimental and theoretical elucidation of the mechanism
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