Linked Life Data

18303836

Source:http://linkedlifedata.com/resource/pubmed/id/18303836

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
15
pubmed:dateCreated
2008-4-11
pubmed:abstractText
The mechanism for the rhodium-catalyzed decarbonylation of aldehydes was investigated by experimental techniques (Hammett studies and kinetic isotope effects) and extended by a computational study (DFT calculations). For both benzaldehyde and phenyl acetaldehyde derivatives, linear Hammett plots were obtained with positive slopes of +0.79 and +0.43, respectively, which indicate a buildup of negative charge in the selectivity-determining step. The kinetic isotope effects were similar for these substrates (1.73 and 1.77 for benzaldehyde and phenyl acetaldehyde, respectively), indicating that similar mechanisms are operating. A DFT (B3LYP) study of the catalytic cycle indicated a rapid oxidative addition into the C(O)-H bond followed by a rate-limiting extrusion of CO and reductive elimination. The theoretical kinetic isotope effects based on this mechanism were in excellent agreement with the experimental values for both substrates, but only when migratory extrusion of CO was selected as the rate-determining step.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Apr
pubmed:issn
1520-5126
pubmed:author
pubmed:issnType
Electronic
pubmed:day
16
pubmed:volume
130
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
5206-15
pubmed:year
2008
pubmed:articleTitle
The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: a combined experimental and theoretical study.
pubmed:affiliation
Center for Sustainable and Green Chemistry, Department of Chemistry, Building 201, Technical University of Denmark, DK-2800 Lyngby, Denmark.
pubmed:publicationType
Journal Article