Organic-inorganic hybrid materials incorporating phosphorus centres. Evidence for some factors controlling the accessibility of phosphorus centres

Abstract

The accessibility of phosphorus centres incorporated into hybrid organic-inorganic materials prepared from various phosphines bearing two or three hydrolysable SiX₃ groups has been investigated by using some classical reactions at phosphorus centres. Estimation of the yields of the reaction has been established by high power proton decoupling magic angle spinning (HPDEC MAS) solid state ³¹P NMR spectroscopy. It was found that reagents such as H₂O₂, S₈ as well as THF·BH₃ and MeI can reach all the phosphorus centres whatever the starting material. In contrast, remarkable differences of accessibility of phosphorus centres in the studied solids were found for the more bulky reagent THF·W(CO)₅. From these results, it appears that the accessibility of the phosphorus centres depends on the structure of the precursor, the degree of condensation of the polysilsesquioxane network, and the specific surface area of the material.

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