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

Research output: Contribution to journalArticlepeer-review

17 Citations (Scopus)

Abstract

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
Volume333
Issue number2-3
DOIs
Publication statusPublished - 2007 Mar 30

Keywords

  • 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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