How the coordination modes change the performance of Rh-PPh3 for complexes catalyst allyl alcohol hydroformylation: A theoretical study

This paper investigates the effect of coordination modes on the selectivity and activity of hydroformylation catalysts using Rhodium complexes. DFT calculations are performed on monophosphine (1P) and bisphosphine (2P) catalysts to study the impact of different coordination modes on the catalytic cycle of allyl alcohol hydroformylation. The results indicate that the AA insertion step of allyl alcohol affects the selectivity, and the asymmetric structure of Rh-PPh3 complexes leads to a higher l/b ratio (linear/branched ratios). The presence of an extra hydroxyl group in allyl alcohol also contributes to the formation of byproducts. In the AA insertion step, the rate and selectivity determining step, the asymmetric structure (ea-conformer) of Rh-PPh3 complexes leads to a preference of AA rotation and H atom transfer for linear pathway, which brings a higher l/b ratio. [Display omitted] •The full catalytic cycle for allyl alcohol (AA) hydroformylation is explored.•The effects of different isomers are systematically investigated.•The mechanism of coordination modes affecting the l/b ratio is proposed.•The ea-conformer could reduce the formation of by-products in AA insertion step.•The -CH2OH group of AA brings the by-product propionaldehyde.