Ab initio study of the change from η5- to η1-coordination in group 12 dimetallocenes MM′(C5H5)2 with M, M′ = Zn, Cd, Hg

Michael R. Philpott, Yoshiyuki Kawazoe

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17 Citations (Scopus)


For group 12 dimetallocenes, ab initio plane wave density functional theory (DFT) quantum electronic structure calculations predict that the metal atom can move from center η5-C5H5 to edge η1-C5H5 coordination with increase in atomic number. Systems studied include homo- and hetero-dimetallocene systems M2Cp2 and ZnMCp2 (where Cp = C5H5) in staggered and eclipsed initial configurations, and M is a group 12 atom Zn, Cd or Hg. The electronic change that drives the geometrical change is explored in calculations of the total charge density, partial charge densities of Kohn-Sham levels and the electron localization function (ELF). The zinc atoms prefer central η5-C5H5 coordination, cadmium an off center position and mercury the edge displaced η1-C5H5 coordination. In this latter configuration the nearest carbon atom shows signs of sp3-hybridization and the other four carbons adopt a cis-butadiene-like structure. In the hetero-systems we find distinct geometries with each M-Cp unit adopting the coordination of the homo-dimetallocene.

Original languageEnglish
Pages (from-to)201-207
Number of pages7
JournalChemical Physics
Issue number2-3
Publication statusPublished - 2007 Mar 30


  • Cadmous
  • Cd
  • Density functional theory (DFT)
  • Dimetallocene
  • Dizincocene
  • Electron localization function (ELF)
  • Electronic structure
  • Hg
  • Kohn-Sham level
  • Mercurous
  • Partial charge density
  • Quantum electronic structure
  • Zincous
  • Zn
  • Zn(η-CH)
  • Zn(η-CH)

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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