Rational design of efficient steric catalyst for isomerization of 2-methyl-3-butenenitrile

The catalytic isomerization of 2-methyl-3-butenenitrile (2M3BN), a model reaction in the DuPont process, has been performed using NiL 4 (L=tri- O - p -tolyl phosphite) as a catalyst. The lowered catalytic activity in the isomerization with coexistence of 2-pentenenitrile (2PN) and 2-methyl-2-butenenitrile (2M2BN) indicates that both 2PN and 2M2BN are the catalyst inhibitors , and the quantitative relationship between the conversion of 2M3BN and the content of 2M2BN and 2PN is provided. DFT calculation results suggest that the inhibition effect is attributed to the generation of dead-end intermediates (2PN)NiL 2 and (2M2BN)NiL 2 , both of which take nickel atom out of the catalytic cycle in the isomerization process. To suppress the inhibition effect, new catalytic intermediates are rationally designed based on their computational %V bur . An efficient method that adding extra ligand 1, 5-bis(diphenylphosphino)pentane (dppp5) to the NiL 4 catalyst is selected experimentally. Compared to the results obtained with NiL 4 as catalyst, the (dppp5)NiL 2 increases the conversion of 2M3BN from 74.5 % to 93.4 % at 3 h of reaction and provides a high selectivity to 3PN (> 98 %) at optimal conditions.