Hydroformylation, hydrogenation, and isomerization of olefins over polymer-immobilized rhodium complexes

Journal Article · Tue Jan 31 23:00:00 EST 1978 · J. Catal.; (United States)

DOI:https://doi.org/10.1016/0021-9517(78)90286-5· OSTI ID:5864133

Arai, H

Silica gel was coated with styrene-divinylbenzene copolymer, the polymer brominated, treated with diphenylphosphide, and then treated with Rh/sub 2/(CO)/sub 4/Cl/sub 2/ to form a complex fixed via rhodium-phosphorus coordination to the polymer. Catalysts prepared by two different polymerization techniques and containing 3.1 and 6.5% rhodium were tested at 130/sup 0/C for hydroformylation, hydrogenation, and isomerization activity for ethylene, propylene, and 1-butene. The hydroformylation results were the same as reported in the literature for the homogeneous rhodium catalyst RhH(CO)/sub 2/(PPh/sub 3/)/sub 2/ (Ph = phenyl) and a similar hydride transfer mechanism was assumed. In the absence of carbon monoxide, only hydrogenation occurred and 100% conversion was obtained at 100/sup 0/C. The reaction orders with respect to carbon monoxide were -0.6 for hydroformylation, -1.1 to -1.3 for hydrogenation, and -1.3 to -1.5 for isomerization, (i.e., the reactions were strongly inhibited by carbon monoxide). Cis- and trans-2-butene were not converted to the corresponding aldehyde. The mechanism was further elucidated by transient response experiments. Graphs, tables, and 22 references.

• Research Organization: Univ. of Tokyo, Japan
• OSTI ID: 5864133
• Journal Information: J. Catal.; (United States), Journal Name: J. Catal.; (United States) Vol. 51:2; ISSN JCTLA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
BROMINATION
CARBONYLATION
CATALYST SUPPORTS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
ETHYLENE
HALOGENATION
HIGH TEMPERATURE
HYDROCARBONS
HYDROGENATION
ISOMERIZATION
KINETICS
MEDIUM TEMPERATURE
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
REACTION KINETICS
RHODIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES