Metal-assisted hydroformylation on a SiO sub 2 -attached Rh dimer. In situ EXAFS and FT-IR observations of the dynamic behaviors of the dimer site
- Univ. of Tokyo (Japan)
- National Chemical Lab. for Industry, Ibaraki (Japan)
- Inst. for Molecular Science, Aichi (Japan)
trans-(Rh(C{sub 5}Me{sub 5})(CH{sub 3})){sub 2}({mu}-CH{sub 2}){sub 2} was supported on the SiO{sub 2} surface by the reaction with OH groups of SiO{sub 2} at 313 K, followed by evacuation at 373 K. In this attaching reaction, the Rh dimer complexes were bound to the SiO{sub 2} surface through Rh-O(surface) bonds, losing one CH{sub 3} ligand and one C{sub 5}Me{sub 5} ligand per Rh dimer. The attached Rh dimers were found to be more active and selective than a conventionally prepared Rh/SiO{sub 2} catalyst. The structure change of the Rh dimer sites in each reaction step for catalytic hydroformylation was followed by means of in-situ FT-IR and in situ EXAFS techniques. The Rh-Rh bond in the attached Rh dimers (Rh-Rh = 0.262 nm) was cleaved by CO adsorption to form monomer pairs (Rh(C{sub 2}H{sub 5})(CO){sub 2}(O-Si) + Rh(C{sub 5}Me{sub 5})(O-Si)). Heating the monomer pairs to 423 K under vacuum resulted in CO insertion, with new peaks exhibited at 1,710 and 1,394 cm{sup {minus}1} due to the acyl ligand.
- OSTI ID:
- 5955451
- Journal Information:
- Journal of the American Chemical Society; (United States), Vol. 112:25; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ETHYLENE
ACYLATION
RHODIUM COMPLEXES
CATALYTIC EFFECTS
CATALYST SUPPORTS
CYCLOPENTADIENE
DIMERS
FORMATES
FOURIER TRANSFORM SPECTROMETERS
INFRARED SPECTRA
LIGANDS
MOLECULAR STRUCTURE
REACTION INTERMEDIATES
SILICON OXIDES
ALKENES
CARBOXYLIC ACID SALTS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKENES
DIENES
HYDROCARBONS
MEASURING INSTRUMENTS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POLYENES
SILICON COMPOUNDS
SPECTRA
SPECTROMETERS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties