In silico investigation of ligand-regulated palladium-catalysed formic acid dehydrative decomposition under acidic conditions

Abstract

In silico investigation of ligand-regulated palladium-catalysed formic acid dehydrative decomposition to carbon monoxide under acidic conditions was conducted. The contribution from the pyridyl group implanted in pytbpx ligand on enhancing the activity of palladium catalyst and the specific role of para-toluenesulfonic acid as the promoter of dehydration were uncovered.

Palladium-catalyzed generation of CO from formic acid for alkoxycarbonylation of internal alkenes involves a PTSA-assisted NH–Pd mechanism: a DFT mechanistic study

“…According to the energetic span model describing a catalytic cycle introduced by Shaik and Kozuch, 39 TSB2 and B4 in Fig. 2 Similar examples of the in situ base mechanism have been reported by Liu et al 40 and Crawford et al 41 More recently, Shen et al 42 reported the computational studies on the decomposition of HCOOH to CO catalyzed by Pd-py t bpx. They also found that the pyridyl group and PTSA played key roles in this reaction; however, they supposed that no PTSA was involved in the dehydration step, because when PTSA acts as a spectator, the extra hydrogen bond would elevate the barrier.…”