Dynamical Density Functional Study of Acetylene to Vinylidene Isomerization in (Cp)(CO)2Mn(HCCH) (Articolo in rivista)

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  • Dynamical Density Functional Study of Acetylene to Vinylidene Isomerization in (Cp)(CO)2Mn(HCCH) (Articolo in rivista) (literal)
Anno
  • 2002-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/om010943k (literal)
Alternative label
  • Filippo De Angelis, Antonio Sgamellotti, Nazzareno Re (2002)
    Dynamical Density Functional Study of Acetylene to Vinylidene Isomerization in (Cp)(CO)2Mn(HCCH)
    in Organometallics
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Filippo De Angelis, Antonio Sgamellotti, Nazzareno Re (literal)
Pagina inizio
  • 2715 (literal)
Pagina fine
  • 2723 (literal)
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  • http://pubs.acs.org/doi/abs/10.1021/om010943k (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 21 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 9 (literal)
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  • 13 (literal)
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  • Filippo De Angelis, Antonio Sgamellotti:Istituto di Scienze e Tecnologie Molecolari (ISTM-CNR) 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
  • Dynamical Density Functional Study of Acetylene to Vinylidene Isomerization in (Cp)(CO)2Mn(HCCH) (literal)
Abstract
  • The acetylene to vinylidene isomerization in (Cp)(CO)2Mn(HCCH) has been investigated by both static and dynamic density functional calculations. The potential energy surface for the conversion of coordinated acetylene to vinylidene has been analyzed by a gradient-corrected DFT approach. The ?1-vinylidene complex has been found 9.0 kcal mol-1 more stable than the acetylene complex and is the thermodynamically most stable species of this reaction system. An unprecedented ?2-vinylidene species has been characterized and found 38.4 kcal mol-1 higher than the corresponding ?1-isomer. The direct 1,2 hydrogen shift, proceeding via an agostic intermediate, is the energetically most favorable path, with a free energy barrier of 27.3 kcal mol-1. The higher barrier computed for the oxidative addition leading to the corresponding alkynylhydrido complex (35.0 kcal mol-1) rules out the intermediacy of such a species in the investigated process. Dynamics simulations have also been performed on the (Cp)(CO)2Mn(HCCH) complex in order to study the detailed features of the possible acetylene to vinylidene conversion pathways and show that the isomerization effectively takes place through a direct 1,2 hydrogen shift from the agostic intermediate. (literal)
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