Linked Life Data

14613129

Source:http://linkedlifedata.com/resource/pubmed/id/14613129

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pubmed-article:14613129rdf:typepubmed:Citationlld:pubmed
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pubmed-article:14613129pubmed:issue21lld:pubmed
pubmed-article:14613129pubmed:dateCreated2003-11-12lld:pubmed
pubmed-article:14613129pubmed:abstractTextThermal reaction of white phosphorus with [(triphos)RhH(3)] (1) in THF affords [(triphos)Rh(eta(1):eta(2)-P(4)H)] (2), triphos=MeC(CH(2)PPh(2))(3). Similar complexes [(triphos)Rh(eta(1):eta(2)-P(4)R)] (R=Me (7), Et (8), Ph (9)) also form at lower temperature by the reaction of P(4) and [(triphos)Rh(R)(eta(2)-C(2)H(4))] with elimination of ethene. In contrast, a double-insertion process follows the reaction of [(triphos)Rh(H)(eta(2)-C(2)H(4))] and P(4) to generate tetraphosphido ethyl complex 8. Compounds 2, 7, 8 and 9 are thermally unstable and eventually decompose into the cyclotriphosphorus complex [(triphos)Rh(eta(3)-P(3))] (3) plus other unidentified phosphorus-containing species. Otherwise, PH(3) or PH(2)R is generated in the presence of H(2). The formation of PH(3) and 3 is quantitative starting from the precursor 2. The electrophilic attack of MeOTf or HBF(4) on the P(4)R ligand in the complexes 2, 7-9 is regioselective, and yields a cationic product of formula [(triphos)Rh(eta(1):eta(2)-P(4)RR')](+). The direct attack on the substituted p-R phosphorus atom is demonstrated by crossing experiments. Complexes of the latter type have been isolated in the solid state for the combinations R=H and R'=Me (11) or R=Ph and R'=Me (12). The latter species, [(triphos)Rh(eta(1):eta(2)-P(4)PhMe')]OTf.2 CH(2)Cl(2) (OTf=triflate), has been characterised by X-ray methods. The geometry at the metal is better described as a trigonal bipyramidal than pseudo-octahedral. In fact, the P(4)RR' unit acts as a bidentate ligand with its exocyclic PR(2) donor group and the endocyclic, dihapto-coordinated Pdbond;P linkage. The latter group lies in the equatorial plane, in a similar way to a classic olefin ligand that is coordinated to a butterfly-shaped L(4)M fragment (M=d(8)). DFT calculations on a model of 2 and all possible protonated isomers confirm that double substitution at the exocyclic P-donor positions of the open P(4) unit is energetically favoured. A multinuclear and multidimensional NMR analysis confirms that this structure is maintained in solution for both the parent and the protonated compounds.lld:pubmed
pubmed-article:14613129pubmed:languageenglld:pubmed
pubmed-article:14613129pubmed:journalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:14613129pubmed:statusPubMed-not-MEDLINElld:pubmed
pubmed-article:14613129pubmed:monthNovlld:pubmed
pubmed-article:14613129pubmed:issn0947-6539lld:pubmed
pubmed-article:14613129pubmed:authorpubmed-author:IencoAndreaAlld:pubmed
pubmed-article:14613129pubmed:authorpubmed-author:MealliCarloClld:pubmed
pubmed-article:14613129pubmed:authorpubmed-author:PeruzziniMaur...lld:pubmed
pubmed-article:14613129pubmed:authorpubmed-author:Wolmershäuser...lld:pubmed
pubmed-article:14613129pubmed:authorpubmed-author:BarbaroPierlu...lld:pubmed
pubmed-article:14613129pubmed:authorpubmed-author:VizzaFrancesc...lld:pubmed
pubmed-article:14613129pubmed:authorpubmed-author:SchererOtto...lld:pubmed
pubmed-article:14613129pubmed:authorpubmed-author:SchmittGuidoGlld:pubmed
pubmed-article:14613129pubmed:issnTypePrintlld:pubmed
pubmed-article:14613129pubmed:day7lld:pubmed
pubmed-article:14613129pubmed:volume9lld:pubmed
pubmed-article:14613129pubmed:ownerNLMlld:pubmed
pubmed-article:14613129pubmed:authorsCompleteYlld:pubmed
pubmed-article:14613129pubmed:pagination5196-210lld:pubmed
pubmed-article:14613129pubmed:dateRevised2009-8-4lld:pubmed
pubmed-article:14613129pubmed:year2003lld:pubmed
pubmed-article:14613129pubmed:articleTitleActivation and functionalization of white phosphorus at rhodium: experimental and computational analysis of the [(triphos)Rh (eta1:eta2-P4RR')]Y complexes (triphos=MeC(CH2PPh2)3; R=H, Alkyl, Aryl; R'=2 electrons, H, Me).lld:pubmed
pubmed-article:14613129pubmed:affiliationIstituto di Chimica dei Composti Organometallici, ICCOM-CNR, Via Madonna del Piano, Polo Scientifico di Sesto Fiorentino, 50018 Sesto Fiorentino, Italy.lld:pubmed
pubmed-article:14613129pubmed:publicationTypeJournal Articlelld:pubmed