Evolution of the dizincocene metal-metal bond in the series Zn2L2 where L = H, CH3, F, η5-C5H5

Michael R. Philpott, Yoshiyuki Kawazoe

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Ab initio plane-wave-based density functional calculations for the molecules Zn2L2 with the ligands L = H, CH3, F, η5-C5H5 (cyclopentadienyl Cp) show how the ZnZn and ZnL bonds evolve to dimetallocene from simple H to the electronically and spatially extended Cp ligand. The metal-metal bond distances (pm) decrease in the order: 240.2 (H), 239 (CH3), 230.4 (F), 230 (Cp) compared to distances: 266 (Zn metal), 246 (Zn22+), 230.5 (crystalline Zn2[C5(CH3)5]2). Analysis is supported by calculation of the total charge and partial charge density distributions and the electron localization function (ELF). In the dizinc region, the ELF consists of a separate ring (torus) and mid-bond axis basin. For molecules with the ligands H, CH3, and F, the mid-bond basin attractor appears on the bond axis at higher ELF followed at lower values by the ring. For Cp, the reverse is true. In the Cp compound, the bonding from ring to metal atom involves both sigma σ-contributions with s-, p-, and d-components and π-contributions with p- and d-components. In the Cp compound, the ELF shows some differentiation in the CC bonding within the C5 ring towards three single C-C and two double C{double bond, long}C bonds.

Original languageEnglish
Pages (from-to)113-123
Number of pages11
JournalJournal of Molecular Structure: THEOCHEM
Volume776
Issue number1-3
DOIs
Publication statusPublished - 2006 Nov 20

Keywords

  • Density functional theory
  • Dizincocene
  • Electron localization function (ELF)
  • Electronic structure
  • Kohn-Sham level
  • Partial charge density
  • Quantum electronic structure
  • Zincous ion Zn
  • Zn(CH)
  • Zn(CH)
  • ZnF
  • ZnH

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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