Metal-metal bond formation between [n]metallocenophanes: Synthesis and characterisation of a dicarba[2]ruthenocenophanium dimer

Andrew D. Russell, Joe B. Gilroy, Kevin Lam, Mairi F. Haddow, Jeremy N. Harvey, William E. Geiger, Ian Manners

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

The redox properties of dicarba[2]ruthenocenophane were investigated using cyclic voltammetry (CV), and the results compared to those reported for ruthenocene. In the presence of the weakly-coordinating supporting electrolyte the latter exhibited a partially reversible oxidation wave corresponding to the formation of the ruthenocenium ion. This ruthenocenium ion exists in equilibrium with the metal metal-bonded dimer dication, as demonstrated in situ by voltammetry and NMR spectroscopy experiments. Under identical experimental conditions, CV scans of dicarba[2]ruthenocenophane show that it undergoes an irreversible one-electron oxidation. Bulk anodic electrolysis confirmed the one-electron oxidation of dicarba[2]ruthenocenophane , its exclusive conversion to the single product, and the subsequent quantitative reduction of that product back to dicarba[2]ruthenocenophane. Unlike the highly temperature and concentration-dependent voltammetry of ruthenocene, that of dicarba[2]ruthenocenophane varies little with changes in the medium.

Original languageEnglish
Pages (from-to)8000-8003
Number of pages4
JournalChemistry - A European Journal
Volume18
Issue number26
DOIs
Publication statusPublished - Jun 25 2012

Keywords

  • dimerisation
  • electrochemistry
  • metal-metal bonding
  • metallocenophanes
  • strained compounds

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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