Three Reactions, One Catalyst: A Multi-Purpose Platinum(IV) Complex and its Silica-Supported Homologue for Environmentally Friendly Processes

摘要

Although platinum nanoparticles and complexes -especially of Pt(0) and Pt(II)- are well known catalysts, siloxane-based platinum complexes are rarely reported. Herein, a Platinum(IV) complex of 4-aminopyridinium-modified disiloxane was prepared and characterized by medium and far infrared spectroscopy, NMR and EDX. The formation of the complex was monitored by UV-Vis spectroscopy, which showed the high affinity and selectivity of this ligand for Pt, with a stability constant of 7.53 center dot 10(3) M-1. The catalytic activity of the siloxane-based complex was tested in three types of reactions: reduction of p-nitrophenol, oxidation of glucose and starch, and hydrosilylation. The hydrophobic behavior of the permethylated disiloxane moiety ensures good hydrolytic stability, while the N-donor ligand stabilizes the in-situ formed Pt nanoparticles. The generation of Pt nanoparticles during p-nitrophenol reduction was confirmed by TEM and SEM. Contrary to most reports, the aerobic oxidation of mono- and polysaccharides occurred without oxidation agents or mediators added, in mild conditions, at room temperature and pH similar to 9. The same metal complex was found active in hydrosilylation of vinyl-siloxanes with temperature-modulated rate, thus being useful in silicone cross-linking systems without the need of inhibitors. The method was adapted to one-pot synthesis of silica-supported Pt(IV) complex, which acted as efficient and reusable heterogeneous hydrosilylation catalyst, limiting the contamination of the product with Pt. This approach is promising for superior valorization of scarcely available and expensive platinum metal. By the same method, multifunctional soluble complexes and mesoporous silica may be obtained, with tunable catalytic performance.