New hybrid bidentate ligands as precursors for smart catalysts.

1-Phosphanorbornadiene derivatives were grafted onto various periodically organized mesoporous powders, including a new zirconia/silica mixed oxide synthesized by aerosol techniques. After complexation with the [Rh(CO)2]+ fragment, these materials were revealed to be more active in olefin hydrogenation than their homogeneous counterparts. The reasons for this higher activity are discussed in the light of theoretical modeling. Various surface treatments, such as esterification, drying, and functionalization with PhSi(OEt)3, provided insights into the nature and mechanism of formation of the active species. Zirconia-based materials were found to be active in internal olefin hydroformylation. Investigation of the mechanism of this reaction shows that the isomerization step is catalyzed by the Lewis acidic support, whereas the hydroformylation step is driven by the rhodium catalyst. Dissociation of these two steps leads to enhancement of activity.