Silica-surface reorganization during organotin grafting evidenced by 119Sn DNP SENS: a tandem reaction of gem-silanols and strained siloxane bridges
Literature Information
Matthew P. Conley, Aaron J. Rossini, Aleix Comas-Vives, Maxence Valla, Gilles Casano, Olivier Ouari, Paul Tordo, Anne Lesage, Lyndon Emsley, Christophe Copéret
Grafting reactive molecular complexes on dehydroxylated amorphous silica is a strategy to develop “single-site” heterogeneous catalysts. In general, only the reactivity of isolated silanols is invoked for silica dehydroxylated at 700 °C ([SiO2-700]), though ca. 10% of the surface silanols are in fact geminal Q2-silanols. Here we report the reaction of allyltributylstannane with [SiO2-700] and find that the geminal Q2-silanols react to form products that would formally arise from vicinal Q3-silanols that are not present on [SiO2-700], indicating that a surface rearrangement occurs. The reorganization of the silica surface is unique to silica dehydroxylated at 700 °C or above. The findings were identified using Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) combined with DFT calculations.
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