Surface organometallic chemistry of main group elements: selective synthesis of silica supported [triple bond Si-OB(C(6)F(5))(3)](-)[HNEt(2)Ph](+)

The reaction of the Lewis acid B(C(6)F(5))(3) with silanol groups of silica surfaces, dehydroxylated at different temperatures (300, 500, 700, and 800 degrees C), has been investigated in presence of the Br?nsted base NEt(2)Ph. The structure of the resulting modified silica supports triple bond Si-OB(C(6)F(5))(3)](-)HNEt(2)Ph](+) (1) has been carefully identified by IR and multinuclear solid-state NMR spectroscopies, isotopic (2)H and (18)O labeling, elemental analysis, molecular modeling, and comparison with synthesized molecular models. Highly dehydroxylated silica surfaces were required to transform selectively each silanol group into unique triple bond Si-OB(C(6)F(5))(3)](-)HNEt(2)Ph](+) fragments. For lower dehydroxylation temperatures, two sorts of surface sites were coexisting on silica: the free silanol groups triple bond SiOH] and the ionic species 1.