Source:http://linkedlifedata.com/resource/pubmed/id/18061923
| Subject | Predicate | Object | Context |
|---|---|---|---|
| pubmed-article:18061923 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:18061923 | lifeskim:mentions | umls-concept:C1261552 | lld:lifeskim |
| pubmed-article:18061923 | lifeskim:mentions | umls-concept:C0044554 | lld:lifeskim |
| pubmed-article:18061923 | pubmed:issue | 6 | lld:pubmed |
| pubmed-article:18061923 | pubmed:dateCreated | 2008-2-18 | lld:pubmed |
| pubmed-article:18061923 | pubmed:abstractText | The rate-determining step in the hydroformylation of 1-octene, catalysed by the rhodium-Xantphos catalyst system, was determined by using a combination of experimentally determined (1)H/(2)H and (12)C/(13)C kinetic isotope effects and a theoretical approach. From the rates of hydroformylation and deuterioformylation, a small (1)H/(2)H isotope effect of 1.2 was determined for the hydride moiety of the rhodium catalyst. (12)C/(13)C isotope effects of 1.012(1) and 1.012(3) for the alpha-carbon and beta-carbon atoms of 1-octene were determined, respectively. Both quantum mechanics/molecular mechanics (QM/MM) and full quantum mechanics calculations were carried out on the key catalytic steps, for "real-world" ligand systems, to clarify whether alkene coordination or hydride migration is the rate-determining step. Our calculations (21.4 kcal mol(-1)) quantitatively reproduce the experimental energy barrier for CO dissociation (20.1 kcal mol(-1)) starting at the (bisphosphane)RhH(CO)(2) resting state. The barrier for hydride migration lies 3.8 kcal mol(-1) higher than the barrier for CO dissociation (experimentally determined trend approximately 3 kcal mol(-1)). The computed (1)H/(2)H and (12)C/(13)C kinetic isotope effects corroborate the results of the energy analysis. | lld:pubmed |
| pubmed-article:18061923 | pubmed:language | eng | lld:pubmed |
| pubmed-article:18061923 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:18061923 | pubmed:status | PubMed-not-MEDLINE | lld:pubmed |
| pubmed-article:18061923 | pubmed:issn | 0947-6539 | lld:pubmed |
| pubmed-article:18061923 | pubmed:author | pubmed-author:KamerPaul C... | lld:pubmed |
| pubmed-article:18061923 | pubmed:author | pubmed-author:van... | lld:pubmed |
| pubmed-article:18061923 | pubmed:author | pubmed-author:BoCarlesC | lld:pubmed |
| pubmed-article:18061923 | pubmed:author | pubmed-author:CarbóJorge... | lld:pubmed |
| pubmed-article:18061923 | pubmed:author | pubmed-author:EichelsheimTa... | lld:pubmed |
| pubmed-article:18061923 | pubmed:author | pubmed-author:ZuidemaErikE | lld:pubmed |
| pubmed-article:18061923 | pubmed:author | pubmed-author:EscorihuelaLa... | lld:pubmed |
| pubmed-article:18061923 | pubmed:issnType | lld:pubmed | |
| pubmed-article:18061923 | pubmed:volume | 14 | lld:pubmed |
| pubmed-article:18061923 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:18061923 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:18061923 | pubmed:pagination | 1843-53 | lld:pubmed |
| pubmed-article:18061923 | pubmed:dateRevised | 2009-8-4 | lld:pubmed |
| pubmed-article:18061923 | pubmed:year | 2008 | lld:pubmed |
| pubmed-article:18061923 | pubmed:articleTitle | The rate-determining step in the rhodium-xantphos-catalysed hydroformylation of 1-octene. | lld:pubmed |
| pubmed-article:18061923 | pubmed:affiliation | Van't Hoff Institute for Molecular Sciences, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam,, The Netherlands. | lld:pubmed |
| pubmed-article:18061923 | pubmed:publicationType | Journal Article | lld:pubmed |