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

Journal Article · Mon Jul 06 04:00:00 EDT 1998 · Organometallics

DOI:https://doi.org/10.1021/om9800795· OSTI ID:638337

Gao, H; Angelici, R J ^[1]

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1. Iowa State Univ., Ames, IA (United States). Dept. of Chemistry

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.

• OSTI ID: 638337
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 14 Vol. 17; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
CARBONYLATION
CATALYSTS
OCTENES
ORGANIC SULFUR COMPOUNDS
REACTION KINETICS
RHODIUM COMPOUNDS
SILICA