Influence of electrostatic repulsive force and electron-withdrawing effect in ionic diphosphine on regioselectivity of rhodium-catalyzed hydroformylation of 1-octene

The neutral diphosphine of 1 and the corresponding ionic diphosphine of 2 after quaternization 1 by MeOTf were prepared and investigated as the wide bite angle and bulky steric ligands to control the regioselectivity in Rh(acac)(CO) 2 -catalyzed hydroformylation of 1-octene. As for 2 , due to the electrostatic repulsive force of the two positive charges, the involved two-PPh 2 were located in trans -position with the relatively longer P 1… P 2 distance [8.0231(11)   Å] to prefer to aa-site coordination in trigonal bipyramid H(alkene)Rh(CO)(P–P) intermediate, which renders less bulky steric hindrance for the regioselectivity to linear aldehyde as a result of low L / B ratio of 1.9. Due to the strong electron-withdrawing effect from the positive-charged imidazolium rings on the neighbored P-atoms, 2 with strong π-acceptor ability can develop π-backdonation interaction between Rh and P linkage to favor the dissociation of CO ligand and facilitate the selectivity to nonanals. In contrast, 1 with no electrostatic repulsive effect and less steric hindrance, the two-PPh 2 were able to be conveniently located in cis -position with the relatively shorter P 1… P 2 distance [ P 1… P 2, 6.2096(10)   Å], which corresponded to the preferential linear regioselectivity with L / B   =   7.1. The in situ high pressure spectroscopy analysis indicated that the involvement of 1 in Rh(acac)(CO) 2 -catalyzed hydroformylation of 1-octene could greatly facilitate the formation and stability of the active Rh–H species ( ν 2047   cm −1 ).