18. A self-catalytic role of methanol in PNP-Ru pincer complex catalysed dehydrogenation

Jiang, Y.-Y.; Xu, Z.-Y.; Yu, H.-Z.;* Fu, Y.* Sci. China Chem. 2016, 59, 724–729. Download Link

Abstract: Extracting hydrogen from methanol is a safe and cost-efficient strategy for fuel supply. This process was realized recently at a mild condition with excellent efficiency by ruthenium pincer catalysts. Despite the experimental success, the associated mechanism remains under debate. With the aid of density functional theory (DFT) calculations, an updated and self-consistent mechanism which involves MeOH-catalysed dehydrogenation of ruthenium hydride intermediate and pre-protonation of the pincer ligand was present herein. This mechanism is kinetically favoured over the previously-proposed water- or formicacid-participated ones and more consistent with the optimal experimental condition where strong base and neat methanol solvent are used.