Linked Life Data

16625251

Source:http://linkedlifedata.com/resource/pubmed/id/16625251

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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
17
pubmed:dateCreated
2006-4-20
pubmed:abstractText
The synthesis, characterisation and thermal and photochemical reactivity of Ru(CO)2(PPh3)(dppe) 1 towards hydrogen are described. Compound proved to exist in both fac (major) and mer forms in solution. Under thermal conditions, PPh3 is lost from 1 in the major reaction pathway and the known complex Ru(CO)2(dppe)(H)2 2 is formed. Photochemically, CO loss is the dominant process, leading to the alternative dihydride Ru(CO)(PPh3)(dppe)(H)2 3. The major isomer of 3, viz. 3a, contains hydride ligands that are trans to CO and trans to one of the phosphorus atoms of the dppe ligand but a second isomer, 3b, where both hydride ligands are trans to distinct phosphines, is also formed. On the NMR timescale, no interconversion of 3a and 3b was observed, although hydride site interchange is evident with activation parameters of DeltaH(double dagger) = 95 +/- 6 kJ mol(-1) and DeltaS(double dagger) = 26 +/- 17 J K(-1) mol(-1). Density functional theory confirms that the observed species are the most stable isomeric forms, and suggests that hydride exchange occurs via a transition state featuring an eta2-coordinated H2 unit.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
May
pubmed:issn
1477-9226
pubmed:author
pubmed:issnType
Print
pubmed:day
7
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2072-80
pubmed:year
2006
pubmed:articleTitle
Contrasting photochemical and thermal reactivity of Ru(CO)2(PPh3)(dppe) towards hydrogen rationalised by parahydrogen NMR and DFT studies.
pubmed:affiliation
Department of Chemistry, University of York, Heslington, York, UKYO10 5DD.
pubmed:publicationType
Journal Article