Effects of Void Environment and Acid Strength on Alkene Oligomerization Selectivity

The effects of channel connectivity, void environment, and acid strength on the relative rates of oligomerization, β-scission, and isomerization reactions during light alkene conversion (ethene, propene, isobutene; 2–400 kPa alkene; 473–533 K) were examined on microporous (TON, MFI, MOR, BEA, FAU) and mesoporous (amorphous silica–alumina (SiAl), MCM-41, Keggin POM) Brønsted acids with a broad range of confining voids and acid strength. Skeletal and regioisomers equilibrate under all conditions of pressure and conversion and on all catalysts, irrespective of their acid strength, void size, or framework connectivity, consistent with rapid hydride and methyl shifts of alkoxides intermediates and with their fast adsorption–desorption steps. Such equilibration is evident from detailed chemical speciation of the products and also from intramolecular isotopic scrambling in all oligomers formed from 2- 13 C-propene on TON, MFI, SiAl, and POM clusters. Previous claims of kinetic control of skeletal isomers in oligomerization catalysis through shape-selective effects conferred by void environments may have used inaccurate tabulated thermodynamics, as we show in this study. The void environment, however, influences the size distribution of the chains formed in these acid-catalyzed alkene reactions. One-dimensional microporous aluminosilicates predominantly form true oligomers, those expected from dimerization and subsequent oligomerization events for a given reactant alkene; such chains are preserved because they cannot grow to sizes that would inhibit their diffusion through essentially cylindrical channels in these frameworks. Amorphous SiAl and colloidal silica-supported POM clusters contain acid sites of very different strength; both exhibit size variations across the void space, but at length scales much larger than molecular diameters, thus preserving true oligomers by allowing them to egress the void before β-scission events. Mesoporous acids of very different strength (POM, SiAl) give similar true isomer selectivities, as also observed on MFI structures with different heteroatoms (X-MFI, where X = Al, Ga, Fe, B), which also differ in acid strength; this insensitivity reflects oligomerization and β-scission reactions that involve similar ion-pair transition states and therefore depend similarly on the stability of the conjugate anion. Three-dimensional microporous frameworks contain voids larger than their interconnecting paths, an inherent consequence of intersecting channels and cage–window structures. As a result, oligomers can reach sizes that restrict their diffusion through the interconnections, until β-scission events form smaller and faster diffusing chains. These undulations are of molecular dimensions and their magnitude, which is defined here as the ratio of the largest scale to the smallest scale along intracrystal diffusion paths, determines the extent to which oligomerization–scission cycles contribute to the size distribution of products. These contributions are evident in the extent to which chain size and the number of 13 C atoms in each molecule formed from 2- 13 C-propene approach their binomial distributions, as they do on microporous acids with significant undulations. The general nature of these conclusions is evident from the similar effects of void shape and connectivity and of acid strength on selectivity for ethene, propene, and isobutene reactants.