Adsorption at the liquid-liquid interface in the biphasic rhodium catalyzed hydroformylation of olefins promoted by...

Using molecular dynamics (MD) simulations, we investigate the interfacial distribution of partners involved in the phase transfer rhodium catalyzed hydroformylation of olefins promoted by beta-cyclodextrins (beta-CDs). The beta-CDs, the reactant (alkene), product (aldehyde), several rhodium complexes (the catalyst, its precursor, and its alkene adduct) are simulated at the water-"oil" interface, where oil is represented by chloroform or hexane. It is shown that unsubstituted beta-CD and its 6-methylated and 2,6-dimethylated analogues adsorb at the interface, whereas the liposoluble permethylated CD does not. The precursor of the catalyst [RhH(CO)(TPPTS)3]9- (with triphenylphosphine trisulfonated TPPTS3- ligands) sits in water, but the less charged [RhH(CO)(TPPTS)2]6- catalyst and the [RhH(CO)(TPPTS)2(alkene)]6- reaction intermediate are clearly surface active. The TPPTS3- anions also concentrate at the interface, where they adopt an amphiphilic conformation, forming an electrical double layer with their Na+ counterions. Thus, the most important key partners involved in the hydroformylation reaction concentrate at the interface, thereby facilitating the reaction, a process which may be further facilitated upon complexation by CDs. These results point to the importance of adsorption at the liquid-liquid interface in the two-phase hydroformylation reaction of olefins promoted by beta-CDs and provide microscopic pictures of this peculiar region of the solution.