Abstract
AbstractSurface rhodium siloxide phosphine complexes have been synthesized directly by condensation of the molecular precursor Rh(cod)(PR3)(OSiMe3) [R=Cy (1), Ph (2), iPr(3); cod=1,5‐cyclooctadiene] with silanol groups on silica (Aerosil 200) and their structures have been characterized by 13C, 29Si, and 31P cross‐polarization magic‐angle spinning (CP/MAS) NMR spectroscopy. Such single‐site complexes have been tested for their activity in hydrosilylation of olefins with heptamethyltrisiloxane and poly(hydromethyl‐co‐dimethyl)siloxane. The immobilized catalysts 1–3 all retained their effectiveness even after recycling up to at least five times and mostly up to ten times. Based on the results of CP/MAS NMR measurements, a mechanism of hydrosilylation catalysis by single‐site rhodium siloxide phosphine complexes is proposed, which involves concurrent pathways of oxidative addition and replacement of phosphine by olefins.
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