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Title: Hydroformylation of 1-octene under atmospheric pressure catalyzed by rhodium carbonyl thiolate complexes tethered to silica

Abstract

The silica-tethered rhodium thiolate complex catalysts Rh-S/SiO{sub 2} and Rh-S-P/SiO{sub 2} were prepared by the condensation of SiO{sub 2} with Rh{sub 2}[{mu}-S(CH{sub 2}){sub 3}Si(OCH{sub 3}){sub 3}]{sub 2}(CO){sub 4} (Rh-S) or Rh{sub 2}[{mu}-S(CH{sub 2}){sub 3}Si(OCH{sub 3}){sub 3}]{sub 2}[Ph{sub 2}P(CH{sub 2}){sub 3}Si(OC{sub 2}H{sub 5}){sub 3}]{sub 2}(CO){sub 2} (Rh-S-P). These tethered complex catalysts exhibit high activity for the hydroformylation of 1-octene in the presence of phosphine donor ligands under the mild conditions of 60 C and 1 atm. IR (DRIFT) spectral studies of the catalysts used indicate that tethered monorhodium dicarbonyl thiolate complexes of the type Rh(SR)(CO){sub 2}(PR{prime}{sub 3}) are the predominant species on the surface for the catalysts that have the highest hydroformylation activity. The catalysts are easily separated from the reaction mixtures, and the Rh-S/SiO{sub 2} catalyst maintains its activity through at least three cycles over a total period of 69 h, during which time there are 1273 (mol of aldehyde/mol of Rh) turnovers. Effects of the phosphine ligand and PR{prime}{sub 3}/Rh mole ratio on the hydroformylation rate, conversion, and chemo- and regioselectivity for aldehyde products were also investigated.

Authors:
;  [1]
  1. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
OSTI Identifier:
638337
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 17; Journal Issue: 14; Other Information: PBD: 6 Jul 1998
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CARBONYLATION; OCTENES; CATALYSTS; RHODIUM COMPOUNDS; ORGANIC SULFUR COMPOUNDS; SILICA; REACTION KINETICS

Citation Formats

Gao, H, Angelici, R J, and Ames Lab., IA. Hydroformylation of 1-octene under atmospheric pressure catalyzed by rhodium carbonyl thiolate complexes tethered to silica. United States: N. p., 1998. Web. doi:10.1021/om9800795.
Gao, H, Angelici, R J, & Ames Lab., IA. Hydroformylation of 1-octene under atmospheric pressure catalyzed by rhodium carbonyl thiolate complexes tethered to silica. United States. doi:10.1021/om9800795.
Gao, H, Angelici, R J, and Ames Lab., IA. Mon . "Hydroformylation of 1-octene under atmospheric pressure catalyzed by rhodium carbonyl thiolate complexes tethered to silica". United States. doi:10.1021/om9800795.
@article{osti_638337,
title = {Hydroformylation of 1-octene under atmospheric pressure catalyzed by rhodium carbonyl thiolate complexes tethered to silica},
author = {Gao, H and Angelici, R J and Ames Lab., IA},
abstractNote = {The silica-tethered rhodium thiolate complex catalysts Rh-S/SiO{sub 2} and Rh-S-P/SiO{sub 2} were prepared by the condensation of SiO{sub 2} with Rh{sub 2}[{mu}-S(CH{sub 2}){sub 3}Si(OCH{sub 3}){sub 3}]{sub 2}(CO){sub 4} (Rh-S) or Rh{sub 2}[{mu}-S(CH{sub 2}){sub 3}Si(OCH{sub 3}){sub 3}]{sub 2}[Ph{sub 2}P(CH{sub 2}){sub 3}Si(OC{sub 2}H{sub 5}){sub 3}]{sub 2}(CO){sub 2} (Rh-S-P). These tethered complex catalysts exhibit high activity for the hydroformylation of 1-octene in the presence of phosphine donor ligands under the mild conditions of 60 C and 1 atm. IR (DRIFT) spectral studies of the catalysts used indicate that tethered monorhodium dicarbonyl thiolate complexes of the type Rh(SR)(CO){sub 2}(PR{prime}{sub 3}) are the predominant species on the surface for the catalysts that have the highest hydroformylation activity. The catalysts are easily separated from the reaction mixtures, and the Rh-S/SiO{sub 2} catalyst maintains its activity through at least three cycles over a total period of 69 h, during which time there are 1273 (mol of aldehyde/mol of Rh) turnovers. Effects of the phosphine ligand and PR{prime}{sub 3}/Rh mole ratio on the hydroformylation rate, conversion, and chemo- and regioselectivity for aldehyde products were also investigated.},
doi = {10.1021/om9800795},
journal = {Organometallics},
number = 14,
volume = 17,
place = {United States},
year = {1998},
month = {7}
}