Full Quantum Mechanical Investigation of the Unimolecular versus Bimolecular Acetylene to Vinylidene Rearrangement in the Prototype trans-Cl-Rh(Pi-Pr3)2 Complex (Articolo in rivista)

Type

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

Label

• Full Quantum Mechanical Investigation of the Unimolecular versus Bimolecular Acetylene to Vinylidene Rearrangement in the Prototype trans-Cl-Rh(Pi-Pr3)2 Complex (Articolo in rivista) (literal)

Anno

• 2007-01-01T00:00:00+01:00 (literal)

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

• 10.1021/om7003964 (literal)

Alternative label

• Filippo De Angelis; Antonio Sgamellotti; Nazzareno Re (2007)
  Full Quantum Mechanical Investigation of the Unimolecular versus Bimolecular Acetylene to Vinylidene Rearrangement in the Prototype trans-Cl-Rh(Pi-Pr3)2 Complex
  in Organometallics
  (literal)

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

• Filippo De Angelis; Antonio Sgamellotti; Nazzareno Re (literal)

Pagina inizio

• 5285 (literal)

Pagina fine

• 5288 (literal)

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

• http://pubs.acs.org/doi/abs/10.1021/om7003964 (literal)

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

• 26 (literal)

Rivista

• Organometallics (Rivista)

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

• 4 (literal)

Note

• ISI Web of Science (WOS) (literal)

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

• Istituto CNR di Scienze e Tecnologie Molecolari (ISTM), c/o Dipartimento di Chimica, Università di Perugia, via Elce di Sotto 8, I-06123, Perugia, Italy, and Facoltà di Farmacia, Università G. D'Annunzio, I-66100 Chieti, Italy (literal)

Titolo

• Full Quantum Mechanical Investigation of the Unimolecular versus Bimolecular Acetylene to Vinylidene Rearrangement in the Prototype trans-Cl-Rh(Pi-Pr3)2 Complex (literal)

Abstract

• We report a full quantum mechanical investigation, based on DFT calculations, on the unimolecular and bimolecular alkyne-vinylidene rearrangements in the prototype [Cl-Rh(Pi-Pr3)2(HCCH)] complex, to solve the discrepancy between theory and recent experimental data and to provide a definitive answer concerning the largely debated molecularity issue of the 1,3-shift in d8 metal complexes. We calculate the intramolecular pathway to be kinetically favored over the intermolecular one by 15.0 kcal/mol, in agreement with recent crossover experiments. Comparison of our DFT calculations performed on the real systems with reduced models shows that a full quantum mechanical description of the investigated systems is mandatory for a correct description of their reactivity, owing to the relevant role played by the electron-donating phosphine ligands. (literal)

Prodotto di

• Istituto di scienze e tecnologie molecolari (ISTM) (Istituto)
• Modellistica chimica e sue applicazioni (PM.P07.003.001) (Modulo)

Autore CNR

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

Incoming links:

Prodotto

• Istituto di scienze e tecnologie molecolari (ISTM) (Istituto)
• Modellistica chimica e sue applicazioni (PM.P07.003.001) (Modulo)

Autore CNR di

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

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

• Organometallics (Rivista)