Importance of interfacial adsorption in the biphasic hydroformylation of higher olefins promoted by cyclodextrins: a molecular dynamics study at the decene/water interface

We report herein a molecular dynamics study of the main species involved in the hydroformylation of higher olefins promoted by cyclodextrins in 1-decene/water biphasic systems at a temperature of 350 K. The two liquids form a well-defined sharp interface of approximately 7 A width in the absence of solute; the decene molecules are generally oriented "parallel" to the interface where they display transient contacts with water. We first focused on rhodium complexes bearing water-soluble TPPTS(3-) ligands (where TPPTS(3-) represents tris(m-sulfonatophenyl)phosphine) involved in the early steps of the reaction. The most important finding concerned the surface activity of the "active" form of the catalyst [RhH(CO)(TPPTS)(2)](6-), the [RhH(CO)(2)(TPPTS)(2)](6-) complex, and the key reaction intermediate [RhH(CO)(TPPTS)(2)(decene)](6-) (with the olefin pi-coordinated to the metal center) which are adsorbed at the water side of the interface in spite of their -6 charge. The free TPPTS(3-) ligands themselves are also surface-active, whereas the -9 charged catalyst precursor [RhH(CO)(TPPTS)(3)](9-) prefers to be solubilized in water. The role of cyclodextrins was then investigated by performing simulations on 2,6-dimethyl-beta-cyclodextrin ("CD") and its inclusion complexes with the reactant (1-decene), a reaction product (undecanal), and the corresponding key reaction intermediate [RhH(CO)(TPPTS)(2)(decene)](6-) as guests; they were all shown to be surface-active and prefer the interface over the bulk aqueous phase. These results suggest that the biphasic hydroformylation of higher olefins takes place "right" at the interface and that the CDs promote the "meeting" of the olefin and the catalyst in this peculiar region of the solution by forming inclusion complexes "preorganized" for the reaction. Our results thus point to the importance of adsorption at the liquid/liquid interface in this important phase-transfer-catalyzed reaction.