The molecular structures of ferrocene in the eclipsed (equilibrium) and staggered (saddle-point) conformations have been determined by full geometry optimizations at the levels of second-order Møller–Plesset (MP2) theory, coupled-cluster singles-and-doubles (CCSD) theory and CCSD theory with a perturbative triples correction [CCSD(T)] in a TZV2P+f basis set. Existing experimental results are reviewed. The agreement between the CCSD(T) results and experiment is in all cases excellent; the calculated structure parameters and the barrier to internal rotation of the ligand rings differ from the most accurate experimental values by calculations for single-configuration-dominated transition metal complexes such as ferrocene thus appear to have an accuracy comparable to that observed for molecules containing only first- and second-row atoms, and to be of a quality similar to that obtained experimentally. A comparison with previous DFT results indicates that the B3LYP model gives overall the overall the best DFT results, with a deviation of around 2 pm for the metal–carbon distance and smaller errors for the cyclopentadienyl rings.

The equilibrium structure of ferrocene

CORIANI, Sonia;
2006-01-01

Abstract

The molecular structures of ferrocene in the eclipsed (equilibrium) and staggered (saddle-point) conformations have been determined by full geometry optimizations at the levels of second-order Møller–Plesset (MP2) theory, coupled-cluster singles-and-doubles (CCSD) theory and CCSD theory with a perturbative triples correction [CCSD(T)] in a TZV2P+f basis set. Existing experimental results are reviewed. The agreement between the CCSD(T) results and experiment is in all cases excellent; the calculated structure parameters and the barrier to internal rotation of the ligand rings differ from the most accurate experimental values by calculations for single-configuration-dominated transition metal complexes such as ferrocene thus appear to have an accuracy comparable to that observed for molecules containing only first- and second-row atoms, and to be of a quality similar to that obtained experimentally. A comparison with previous DFT results indicates that the B3LYP model gives overall the overall the best DFT results, with a deviation of around 2 pm for the metal–carbon distance and smaller errors for the cyclopentadienyl rings.
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

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/11368/1692104
 Avviso

Registrazione in corso di verifica.
La registrazione di questo prodotto non è ancora stata validata in ArTS.

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 147
  • ???jsp.display-item.citation.isi??? ND
social impact