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Synthesis of Silica-Supported Compact Phosphines and Their Application to Rhodium-Catalyzed Hydrosilylation of Hindered Ketones with Triorganosilanes

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    Synthesis of Silica-Supported Compact Phosphines and Their Application to Rhodium-Catalyzed Hydrosilylation of Hindered Ketones with Triorganosilanes
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    Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060−0810, Japan, Catalysis Research Center, Hokkaido University, Sapporo 001−0021, Japan, and Division of Natural Sciences, International Christian University, Mitaka, Tokyo 181−8585, Japan
    * To whom correspondence should be addressed. E-mail: [email protected]
    †Faculty of Science, Hokkaido University.
    ‡Catalysis Research Center, Hokkaido University.
    §International Christian University.
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    Organometallics

    Cite this: Organometallics 2008, 27, 24, 6495–6506
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    https://doi.org/10.1021/om800683g
    Published November 18, 2008
    Copyright © 2008 American Chemical Society
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    Abstract

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    Solid-supported phosphine ligands silica−SMAPs {[silica gel 60N]−SMAP (1a) or [CARiACT Q-10]−SMAP (1b)}, which are composed of a caged, compact trialkylphosphine (SMAP) as a ligand and silica gel (silica gel 60N or CARiACT Q-10) as a support, were synthesized through surface functionalization. The supported phosphines (1a,b) were structurally characterized by solid-state 13C, 29Si, and 31P cross-polarization/magic angle spinning (CP/MAS) NMR spectroscopies and N2 adsorption measurements. Complexation of 1a,b with [RhCl(cod)]2 afforded a mono(phosphine)-rhodium complex Silica−SMAP−RhCl(cod) exclusively, even in the presence of excess ligands, as proved by solid-state 13C and 31P CP/MAS NMR spectroscopies and Rh K-edged X-ray absorption fine structure (XAFS) measurements. Heterogeneous catalysts that were prepared from [RhCl(C2H4)2]2 and 1a,b showed exceptionally high catalytic activities for the reaction of sterically hindered ketones (including di-tert-butyl ketone) and triorganosilanes such as Et3SiH and (t-Bu)Me2SiH. The catalyst from 1b showed no leaching of rhodium after reaction and was reusable without decrease of the activity.

    Copyright © 2008 American Chemical Society

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    Supporting Information

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    CP/MAS NMR spectra of 1b (13C, 31P and 29Si) and 6b (13C and 29Si). 31P NMR spectra for Rh/2 mixtures. Nitrogen adsorption−desorption isotherms and pore diameter distributions for silica gel 60N, CARiACT Q-10, 1a and 1b. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Organometallics

    Cite this: Organometallics 2008, 27, 24, 6495–6506
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om800683g
    Published November 18, 2008
    Copyright © 2008 American Chemical Society
    Request reuse permissions

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