Bidentate Disilicate Framework for Bis-Grafted Surface Species

Chemistry. 2021 Aug 19;27(47):12069-12077. doi: 10.1002/chem.202101927. Epub 2021 Jul 29.

Abstract

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(Ot Bu)2 OSi(Ot 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.

Keywords: bis-grafted surface species; disilicate ligands; grafting on silicon atoms; six-membered rings; surface organometallic chemistry.