Carboxylate-assisted C–H activation of phenylpyridines with copper, palladium and ruthenium: a mass spectrometry and DFT study

Abstract

The C–H activation of 2-phenylpyridine, catalyzed by copper(II), palladium(II) and ruthenium(II) carboxylates, was studied in the gas phase. ESI-MS, infrared multiphoton dissociation spectroscopy and quantum chemical calculations were combined to investigate the intermediate species in the reaction. Collision induced dissociation (CID) experiments and DFT calculations allowed estimation of the energy required for this C–H activation step and the subsequent acetic acid loss. Hammett plots constructed from the CID experiments using different copper carboxylates as catalysts revealed that the use of stronger acids accelerates the C–H activation step. The reasoning can be traced from the associated transition structures that suggest a concerted mechanism and the key effect of the carbon–metal bond pre-formation. Carboxylates derived from stronger acids make the metal atom more electrophilic and therefore shift the reaction towards the formation of C–H activated products.