Computational mechanistic studies of ruthenium catalysed methanol dehydrogenation.

Homogeneous ruthenium catalysed methanol dehydrogenation could become a key reaction for hydrogen production in liquid fuel cells. In order to improve existing catalytic systems, mechanistic insight is paramount in directing future studies. Herein, we describe what computational mechanistic research has taught us so far about ruthenium catalysed dehydrogenation reactions. In general, two mechanistic pathways can be operative in these reactions: a metal-centered or a metal-ligand cooperative (Noyori-Morris type) minimum energy reaction pathway (MERP). Discerning between these mechanisms on the basis of computational studies has proven to be highly input dependent, and to circumvent pitfalls it is important to consider several factors, such as solvent effects, metal-ligand cooperativity, alternative geometries, and complex electronic structures of metal centres. This Frontiers article summarizes the reported computational research performed on ruthenium catalyzed dehydrogenation reactions performed in the past decade, and serves as a guide for future research.