A dynamic density functional study of the stepwise migratory insertion of isocyanides into zirconium-carbon bonds anchored to a calix[4]arene moiety (Articolo in rivista)

Type

• Articolo in rivista (Classe)
• Prodotto della ricerca (Classe)

Label

• A dynamic density functional study of the stepwise migratory insertion of isocyanides into zirconium-carbon bonds anchored to a calix[4]arene moiety (Articolo in rivista) (literal)

Anno

• 2002-01-01T00:00:00+01:00 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi

• 10.1021/om020250j (literal)

Alternative label

• Fantacci S., De Angelis F., Sgamellotti A., Re N. (2002)
  A dynamic density functional study of the stepwise migratory insertion of isocyanides into zirconium-carbon bonds anchored to a calix[4]arene moiety
  in Organometallics
  (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

• Fantacci S., De Angelis F., Sgamellotti A., Re N. (literal)

Pagina inizio

• 4090 (literal)

Pagina fine

• 4098 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#url

• http://pubs.acs.org/doi/abs/10.1021/om020250j (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume

• 21 (literal)

Rivista

• Organometallics (Rivista)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali

• 9 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo

• 20 (literal)

Note

• ISI Web of Science (WOS) (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni

• Simona Fantacci , Filippo De Angelis , Antonio Sgamellotti: Istituto CNR di Scienze e Tecnologie Molecolari (ISTM) c/o Dipartimento di Chimica, Università di Perugia, I-06123 Perugia, Italy Nazzareno Re: Facoltà di Farmacia, Università G. D'Annunzio, I-66100 Chieti, Italy (literal)

Titolo

• A dynamic density functional study of the stepwise migratory insertion of isocyanides into zirconium-carbon bonds anchored to a calix[4]arene moiety (literal)

Abstract

• The stepwise migratory insertion of methyl isocyanide into the zirconium-carbon bonds in [calix[4](OMe)2(O)2-ZrMe2] has been investigated by means of both static and dynamic density functional calculations. Dynamics simulations have shown that methyl isocyanide insertion takes place via the initial formation of an ?1-iminoacyl species that is suddenly converted into the more stable ?2-isomer. The energy profiles for the two pathways branching from the initially formed ?2-iminoacyl, i.e., (i) the insertion of a second isocyanide molecule into the residual alkyl group leading to a bis-?2-iminoacyl and (ii) the insertion of the residual alkyl group into the iminoacyl moiety leading to an ?2-bound imine, have been characterized. Formation of the bis-?2-iminoacyl species was found to be thermodynamically favored at low temperature (?G =7.2 vs 6.4 kcal mol-1, ?E = -38.5 vs -12.2 kcal mol-1). However, the large entropic contribution to the barrier for this intermolecular process kinetically favors the intramolecular imine formation at room temperature (?G =11.5 vs 6.4 kcal mol-1), providing a rationale for the experimentally characterized temperature selectivity of the overall reaction. (literal)

Prodotto di

• Istituto di scienze e tecnologie molecolari (ISTM) (Istituto)

Autore CNR

• FILIPPO DE ANGELIS (Persona)
• ANTONIO SGAMELLOTTI (Unità di personale esterno)
• SIMONA FANTACCI (Persona)

Incoming links:

Prodotto

• Istituto di scienze e tecnologie molecolari (ISTM) (Istituto)

Autore CNR di

• FILIPPO DE ANGELIS (Persona)
• SIMONA FANTACCI (Persona)
• ANTONIO SGAMELLOTTI (Unità di personale esterno)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi

• Organometallics (Rivista)