Catalysis of hydrosilylation by well-defined rhodium siloxide complexes immobilized on silica

• Published in: Journal of molecular catalysis. A, Chemical Vol. 310; no. 1; pp. 9 - 16
• Main Authors: Marciniec, Bogdan, Szubert, Karol, Fiedorow, Ryszard, Kownacki, Ireneusz, Potrzebowski, Marek J., Dutkiewicz, Michał, Franczyk, Adrian
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.09.2009; Elsevier
• Subjects: Catalysis; Chemistry; Colloidal state and disperse state; Exact sciences and technology; General and physical chemistry; Hydrosilylation; Immobilized complexes; Porous materials; Rhodium siloxide complexes; Silica supports; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Rhodium siloxide complexes; Hydrosilylation; Silica supports; Immobilized complexes; Binary compound; Transition element complexes; Support; NMR spectrometry; Selectivity; Porous material; Condensation; Precursor; Silica; Supported catalyst; Mechanism; Carbon carbon bond; Catalysis; Structure; Surface complex; Rhodium complex; Catalytic reaction; Mesoporosity; Heterogeneous catalysis; Platinoid Complexes; Aerosil
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/j.molcata.2009.05.013

Well-defined rhodium siloxide surface complexes prepared directly from molecular precursors [{Rh( μ-OSiMe 3)(diene)} 2] characterized by solid-state MAS NMR spectroscopy appear to be highly effective catalysts for hydrosilylation of olefins. Rhodium surface siloxide complexes were prepared directly by condensation of the molecular precursors ([{Rh( μ-OSiMe 3)(cod)} 2], [{Rh( μ-OSiMe 3)(tfb)} 2], [{Rh( μ-OSiMe 3)(nbd)} 2]) with silanol groups on silica surface (Aerosil 200 and SBA-15) and their structures were characterized by 13C and 29Si CP/MAS NMR spectroscopy. Such single-site complexes were tested for their activity in hydrosilylation of carbon–carbon double bonds with triethoxysilane, heptamethyltrisiloxane and poly(hydro,methyl)(dimethyl)siloxane. The best catalyst appeared to be cyclooctadiene ligand-containing rhodium siloxide complex immobilized on Aerosil which was recycled as many as 20 times without loss of activity and selectivity in hydrosilylation of vinylheptamethyltrisiloxane with heptamethyltrisiloxane. On the ground of CP/MAS NMR measurements it was established that the mechanism of hydrosilylation catalyzed by silica-supported rhodium siloxide complexes is different from that for the complexes in the homogeneous system.