Ruthenium(II)-PNN pincer complex catalyzed dehydrogenation of benzyl alcohol to ester: A DFT study

•The dehydrogenation of primary alcohol to ester catalyzed by the ruthenium(II)-PNN pincer complex has been studied.•The catalytic cycle includes three stages.•Two dehydrogenation reactions occur via the β-H elimination mechanism rather than the BDHT mechanism.•At the second stage, the coupling reaction requires alcohol or the ruthenium catalyst as mediator.•The formation of hemiacetal through the alcohol-mediated pathway is kinetically favorable.

The molecular mechanism of the dehydrogenation of primary alcohol to ester catalyzed by the ruthenium(II)-PNN pincer complex Ru(H)(η2-BH4)(PNN), [PNN: (2-(di-tert  -butylphosphinomethyl)-6-(diethlaminomethyl)-pyridine)] has been investigated using density functional theory calculations. The catalytic cycle includes three stages: (stage I) alcohol dehydrogenation to form aldehyde, (stage II) coupling of aldehyde with alcohol to give hemiacetal or ester, and (stage III) hemiacetal dehydrogenation to form ester. Two dehydrogenation reactions occur via the β-H elimination mechanism rather than the bifunctional double hydrogen transfer mechanism, which could be rationalized as the fluxional behavior of the −BH4BH4− ligand. At the second stage, the coupling reaction requires alcohol or the ruthenium catalyst as mediator. The formation of hemiacetal through the alcohol-mediated pathway is kinetically favorable than the ruthenium catalyst-mediated one, which may be attributed to the smaller steric hindrance when the aldehyde approaches the alcohol moiety in the reaction system. Our results would be helpful for experimental chemists to design more effective transition metal catalysts for dehydrogenation of alcohols.

Graphical abstractDensity functional calculations reveal that the dehydrogenation reaction includes three stages. At the first stage, two dehydrogenation reactions occur via the β-H elimination mechanism rather than the bifunctional double hydrogen transfer mechanism. At the second stage, the coupling reaction requires alcohol or the ruthenium catalyst as mediator. The formation of hemiacetal through the alcohol-mediated pathway is kinetically favorable than the ruthenium catalyst-mediated one.Figure optionsDownload full-size imageDownload as PowerPoint slide