Bidentate Disilicate Framework for Bis-Grafted Surface Species

Recent advances in surface organometallic chemistry have enabled the detailed characterization of the surface species in single-site heterogeneous catalysts. However, the selective formation of bis-grafted surface species remains challenging because of the heterogeneity of the supporting surface. Herein, we introduce a metal complex bearing bidentate disilicate ligands, -OSi(O^t Bu)₂ OSi(O^t Bu)₂ O-, as a molecular precursor, which has a silicate framework adjacent to the metal (Pt) center. The grafting of the precursors on silica supports (MCM-41 and CARiACT Q10) proceeded through a substitution reaction on the silicon atoms of the disilicate ligand, which was verified by the detection of isobutene and ^t BuOH as the elimination products, to selectively yield bis-grafted surface species. The chemical structure of the surface species was characterized by solid-state NMR, and the chemical shift values of the ancillary ligands and ¹⁹⁵ Pt nuclei suggested that the bidentate coordination sphere was maintained following grafting.