Dynamical Density Functional Study of the Multistep CO Insertion into Zirconium-Carbon Bonds Anchored to a Calix[4]arene Moiety (Articolo in rivista)

Type

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

Label

• Dynamical Density Functional Study of the Multistep CO Insertion into Zirconium-Carbon Bonds Anchored to a Calix[4]arene Moiety (Articolo in rivista) (literal)

Anno

• 2001-01-01T00:00:00+01:00 (literal)

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

• 10.1021/om010509i (literal)

Alternative label

• S. Fantacci , F. De Angelis , A. Sgamellotti, N. Re (2001)
  Dynamical Density Functional Study of the Multistep CO Insertion into Zirconium-Carbon Bonds Anchored to a Calix[4]arene Moiety
  in Organometallics
  (literal)

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

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

Pagina inizio

• 4031 (literal)

Pagina fine

• 4039 (literal)

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

• http://pubs.acs.org/doi/abs/10.1021/om010509i (literal)

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

• 20 (literal)

Rivista

• Organometallics (Rivista)

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

• 9 (literal)

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

• 19 (literal)

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

• S. Fantacci , F. De Angelis ,A. Sgamellotti: Dipartimento di Chimica e Centro di Studio CNR per il Calcolo Intensivo in Scienze Molecolari, Università di Perugia, I-06123 Perugia, Italy N. Re: Facoltà di Farmacia, Università G. D'Annunzio, I-66100 Chieti, Italy (literal)

Titolo

• Dynamical Density Functional Study of the Multistep CO Insertion into Zirconium-Carbon Bonds Anchored to a Calix[4]arene Moiety (literal)

Abstract

• The multistep migratory insertion reaction of CO into the zirconium-carbon bonds in [calix[4](OMe)2(O)2ZrMe2] has been investigated by means of both static and dynamic density functional calculations. A relatively stable facial CO complex has been observed with a negligible barrier for CO insertion into one of the Zr-Me bonds, leading to the formation of an ?2-acyl complex. The insertion of the residual alkyl group into the acyl moiety, leading to an ?2-bound acetone, has also been investigated, and a small energy barrier, 2.3 kcal/mol, has been found. Dynamics simulations have been performed on the [calix[4](OMe)2(O)2Zr(Me)2]-CO adduct in order to study the detailed features of the whole multistep insertion and show that the migratory insertion leads to the formation of an out-of-plane ?1-acyl complex, which is readily converted into the more stable ?2-acyl isomer within 1.5 ps. The subsequent methyl to acyl migration has been observed within 5 ps, leading to the formation of the ?2-bound acetone by a facial attack of the migrating methyl to the acyl carbon. A comparison with the migratory insertion of CO into the metal-alkyl bond in (Me)2Zr(Cp)2 has been performed, showing substantial differences in the reactivity of the calix[4]arene and bis(cyclopentadienyl) substrates. (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)