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-Pr-3)(2)(HC CH)] 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 d(8) 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.

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

De Angelis, Filippo
;
Sgamellotti, Antonio;Re, Nazzareno
2007

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-Pr-3)(2)(HC CH)] 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 d(8) 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.
2007
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11391/1443100
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 31
  • ???jsp.display-item.citation.isi??? 30
social impact