Linked Life Data

15483704

Source:http://linkedlifedata.com/resource/pubmed/id/15483704

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
20
pubmed:dateCreated
2004-10-14
pubmed:abstractText
The photochemical reaction of Ru(CO)(3)(dppe) and Fe(CO)(3)(dppe)(dppe = Ph(2)PCH(2)CH(2)PPh(2)) with parahydrogen has been studied by in situ-photochemistry resulting in NMR spectra of Ru(CO)(2)(dppe)(H)(2) that show significant enhancement of the hydride resonances while normal signals are seen in Fe(CO)(2)(dppe)(H)(2). This effect is associated with a singlet electronic state for the key intermediate Ru(CO)(2)(dppe) while Fe(CO)(2)(dppe) is a triplet. DFT calculations reveal electronic ground states consistent with this picture. The fluxionality of Ru(CO)(2)(dppe)(H)(2) and Fe(CO)(2)(dppe)(H)(2) has been examined by NMR spectroscopy and rationalised by theoretical methods which show that two pathways for ligand exchange exist. In the first, the phosphorus and carbonyl centres interchange positions while the two hydride ligands are unaffected. A second pathway involving interchange of all three ligand sets was found at slightly higher energy. The H-H distances in the transition states are consistent with metal-bonded dihydrogen ligands. However, no local minimum (intermediate) was found along the rearrangement pathways.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Oct
pubmed:issn
1477-9226
pubmed:author
pubmed:issnType
Print
pubmed:day
21
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
3218-24
pubmed:year
2004
pubmed:articleTitle
The reaction of M(CO)3(Ph2PCH2CH2PPh2)(M = Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products.
pubmed:affiliation
Department of Chemistry, University of York, YO10 5DD, UK.
pubmed:publicationType
Journal Article