Silanol-directed carbonylation

To model the photochemical reaction of Re2(CO)io with silica in the presence of THE, silanolates other than silsesquioxanes [Et3SiOH, PhsSiOH, Ph2Si(OH)2 and (OH)Ph2SiOSiPh2(OH)j with [Re2(CO)8(THE)2] have also been synthesized [148], pointing to the formation of the surface species [((r-=SiO)((r-H)Re2(CO)8j in the above-mentioned reaction with silica. Rhenium carbonyl of the two diol derivatives listed above where both the SiOH have reacted are proposed as models for surface reaction with a vicinal hydroxyl residue, although no direct surface species is reported [148]. 

The proton sponge, l,8-bis(dimethylaminonaphthalene) (DMAN), has been anchored onto amorphous and pure silica MCM-41.[182] DMAN supported on MCM-41 is an excellent base catalyst for the Knoevenagel condensation between benzaldehyde and different active methylene compounds, as well as for the Claisen-Schmidt condensation of benzaldehyde and 2 -hydroxyacetophenone to produce chalcones and flavanones. It was found that the activity of the supported catalyst is directly related to the polarity of the inorganic support. Moreover, the support can also preactivate the reagents by interaction of the carbonyl groups with the weakly acidic silanol groups of MCM-41. This preactivation step enables DMAN, anchored onto MCM-41, to abstract protons with a higher pK than that of the DMAN. 

In terms of availability, number, and nature of surface groups, surface area, pore size, pore volume, and form and size of the particles, silica has been undoubtedly the most preferred inorganic support. Suitable modification is possible via the surface silanol groups, which can react either directly with an appropriate metal complex or with an intermediate ligand group. Direct surface bonding has often been practiced, e. g., for the anchoring of metal carbonyl complexes [14] (eq. (11)), carbonyl clusters [26], polymerization catalysts [21, 62], or other special systems, e. g., 7r-allyl complexes [63] or metalloporphyrins [64]. 

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