2008年12月
Synthesis of Silica-Supported Compact Phosphines and Their Application to Rhodium-Catalyzed Hydrosilylation of Hindered Ketones with Triorganosilanes
ORGANOMETALLICS
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- 巻
- 27
- 号
- 24
- 開始ページ
- 6495
- 終了ページ
- 6506
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1021/om800683g
- 出版者・発行元
- AMER CHEMICAL SOC
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 get 60N or CARiACT Q-10) as a support,'were synthesized through surface functionalization. The supported phosphines (1a,b) were structurally characterized by solid-state (13)C, (29)Si, and (31)P cross-polarization/magic angle spinning (CP/MAS) NMR spectroscopies and N(2) 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 (13)C and (31)P CP/MAS NMR spectroscopies and Rh K-edged X-ray'absorption fine structure (XAFS) measurements. Heterogeneous catalysts that were prepared from [RhCl(C(2)H(4))(2)](2) and 1a,b showed exceptionally high catalytic activities for the reaction of sterically hindered ketones (including di-tertbutyl ketone) and triorganosi lanes such as Et(3)SiH and (t-Bu)Me(2)SiH. The catalyst from 1b showed no leaching of rhodium after reaction and was reusable without decrease of the activity.
- リンク情報
- ID情報
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- DOI : 10.1021/om800683g
- ISSN : 0276-7333
- eISSN : 1520-6041
- ORCIDのPut Code : 28783548
- Web of Science ID : WOS:000261510000020