@prefix prodottidellaricerca: . @prefix istituto: . @prefix prodotto: . istituto:CDS063 prodottidellaricerca:prodotto prodotto:ID39366 . @prefix pubblicazioni: . @prefix unitaDiPersonaleInterno: . unitaDiPersonaleInterno:MATRICOLA7871 pubblicazioni:autoreCNRDi prodotto:ID39366 . unitaDiPersonaleInterno:MATRICOLA1282 pubblicazioni:autoreCNRDi prodotto:ID39366 . @prefix modulo: . modulo:ID2685 prodottidellaricerca:prodotto prodotto:ID39366 . @prefix rdf: . @prefix retescientifica: . prodotto:ID39366 rdf:type retescientifica:ProdottoDellaRicerca , prodotto:TIPO1101 . @prefix rdfs: . prodotto:ID39366 rdfs:label "Alkyl-Rhodium Transition State Stabilities as a Tool to Predict Regio- and Stereoselectivity in the Hydroformylation of Chiral Substrates (Articolo in rivista)"@en . @prefix xsd: . prodotto:ID39366 pubblicazioni:anno "2005-01-01T00:00:00+01:00"^^xsd:gYear . @prefix skos: . prodotto:ID39366 skos:altLabel "
Alagona* G., Ghio C. (2005)
Alkyl-Rhodium Transition State Stabilities as a Tool to Predict Regio- and Stereoselectivity in the Hydroformylation of Chiral Substrates
in Journal of organometallic chemistry (Print)
"^^rdf:HTML ; pubblicazioni:autori "Alagona* G., Ghio C."^^xsd:string ; pubblicazioni:paginaInizio "2339"^^xsd:string ; pubblicazioni:paginaFine "2350"^^xsd:string ; pubblicazioni:numeroVolume "690"^^xsd:string . @prefix ns11: . prodotto:ID39366 pubblicazioni:rivista ns11:ID395055 ; pubblicazioni:note "http://dx.doi.org/10.1016/j.jorganchem.2004.12.038"^^xsd:string ; skos:note "ISI Web of Science (WOS)"^^xsd:string ; pubblicazioni:affiliazioni "IPCF-CNR, Molecular Modeling Lab, Via Moruzzi 1, 56124 Pisa, Italy"^^xsd:string ; pubblicazioni:titolo "Alkyl-Rhodium Transition State Stabilities as a Tool to Predict Regio- and Stereoselectivity in the Hydroformylation of Chiral Substrates"^^xsd:string ; prodottidellaricerca:abstract "A theoretical investigation on the stability of the alkyl rhodium transition states as the key-step determining the regio- and diastereoselective outcomes of the hydroformylation reaction with an unmodified rhodium catalyst (H\u0097Rh(CO)3) has been carried out. The results obtained employing effective core potentials for Rh in the LANL2DZ valence basis set, with the other atoms described at the B3P86/6-31G* level, have been compared to those computed with B3LYP/SBK(d), using effective core potentials for Rh and main group atoms. A number of contaminations between those levels or additional basis functions have also been used. The substrates considered are three related chiral olefins, namely (1-vinyloxy-ethyl)-benzene (1), (1-methyl-but-3-enyl)-benzene (2), and (1-methyl-allyl)-benzene (3). The structural features of the various possible complexes, which show a second chiral center at the inner olefin carbon upon complexation, do not present major changes among the various computational descriptions for each substrate. Significant differences in relative stabilities of the lowest energy transition states can be detected in the case of the ethereal substrate (1), whereas for both chiral alkenes (2 and 3) only very small energy gaps have been computed. In the case of 1 and 2, a quantitative agreement with available experimental results is obtained at the B3P86/6-31G* level, that should allow the prediction of regio- and stereoselectivity for chiral olefins not already screened. The B3LYP/SBK(d) values are comparable to the B3P86/6-31G* ones, although in the case of vinylether (1) the B3LYP/SBK(d) regioisomeric ratio turns out to be critical." ; prodottidellaricerca:prodottoDi modulo:ID2685 , istituto:CDS063 ; pubblicazioni:autoreCNR unitaDiPersonaleInterno:MATRICOLA1282 , unitaDiPersonaleInterno:MATRICOLA7871 . @prefix parolechiave: . prodotto:ID39366 parolechiave:insiemeDiParoleChiave . ns11:ID395055 pubblicazioni:rivistaDi prodotto:ID39366 . parolechiave:insiemeDiParoleChiaveDi prodotto:ID39366 .