Preparation and characterization of organic- inorganic hybrid materials incorporating diphosphino moieties. Study of the accessibility of the phosphorus atoms included into the material

The hydrolysis-polycondensation by the sol-gel process of the aromatic diphosphines (X3SiC6H4)2PC6H4P(C6H4SiX3)2, which are rigid molecules bearing four hydrolysable SiX3 groups (X = OiPr, H), leads to new organic-inorganic hybrid materials, characterized by solid state 13C, 29Si, and 31P NMR spectroscopies. The accessibility of the phosphorus centres incorporated into the xerogel obtained from the diphosphine with X = OiPr has been studied. All the phosphorus atoms reacted quantitatively with H2O2, S8, and CH3I but only 20% with the more bulky reagent W(CO)5·THF. This result is explained by the rigidity of the inorganic network resulting from the high number of hydrolysable Si-OiPr groups in the precursor.Key words : Diphosphines, sol-gel process, xerogels, solid 31P NMR.