Silsesquioxanes as molecular analogues of single-site heterogeneous catalysts

We discuss herein selected examples of metal complexes of polyhedral oligosilses-quioxanes (POSSs) as models of single-site heterogeneous surface catalysts. The utility of these compounds as such models is illustrated when employed as analogues of single-site titanium species supported on a silica surface. Deep insights into structure–functionality relationships can be gained. In particular, it was possible to probe the relationship between accessibility of the reactive centre and turnover frequencies in a manner that is impossible for a purely heterogeneous catalyst. We also report that the partially dehydroxylated SiO2 surface alone is an effective radical polymerization initiation catalyst. This surface reactivity is modelled by the solution reactions between the olefin substrate and two POSSs, the completely condensed triganol prism, Si6Cy6O9 (a6b0, Cy = Cyclohexyl, C6H11), and the incompletely condensed partial cube, Si7Cy7O9(OH)3 (a7b3). The former, with six-membered Si3O3 rings, is a catalyst. The latter, without this feature, is not. Similar reactivity discrimination is observed in the gas phase reactions of these POSSs with the olefin substrate, examined using atmospheric pressure chemical ionization- and collision-induced decomposition spectroscopies. Silsesquioxane a6b0, containing Si3O3 rings, reacts with the olefin, forming grafted olefin monomers and dimers, while this reactivity is not observed with silsesquioxane a7b3.