Production of carbon monoxide and hydrogen from methanol using a ruthenium pincer complex: a DFT study.

To understand the mechanism of the dehydrogenation of methanol to CO and H catalyzed by a ruthenium pincer complex, a density functional theory (DFT) study has been conducted on two different cycles which differ in the substances entering the cycle (methanol (cycle 1) methoxymethanol (cycle 2)). Our calculated results show that both cycles consist of three stages: dehydrogenation of alcohol to aldehyde (stage I); hydrogen formation (stage II); and decarbonylation with the regeneration of the catalyst (stage III). The energy barriers of the rate-determining steps for cycles 1 and 2 are 49.6 and 28.5 kcal mol, respectively. Thus cycle 2 is more energetically feasible. For stage III of cycle 2, our results did not support the mechanism proposed in the experiment (CO release occurs prior to decarbonylation). Instead, we suggested and examined an alternative pathway, that is, decarbonylation occurs prior to CO release. The mechanistic insights gained in the present paper could be beneficial for further designing of these kinds of reactions.