Electrochemistry and computations of stable silylenes and germylenes

Anand Dhiman, Thomas Müller, Robert West, James Y. Becker

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

Stable silylenes, 1 and 2, and germylenes, 3 and 4, have been studied computationally and by cyclic voltammetry (CV). Electron affinities (E A) and ionization potentials (I P) were calculated; the latter agree well with available gas phase photoelectron spectroscopy data. All CV measurements in THF-Bu 4NClO 4 exhibit irreversible waves for all compounds, for both oxidation and reduction processes. However, in l,2-dichlorobenzene-Bu 4NClO 4, the germylene derivative 3 shows a single reversible oxidation couple, whereas 4 exhibits a reversible couple at its second oxidation step, the first one being irreversible. In both cases, the redox couples become irreversible by replacing the electrolyte with either Bu4NBF4 or Bu 4NHSO 4, indicating the importance of the counteranion on the stability of the intermediates. The CV results also show that the unsaturated 1 and 3 are more easily oxidized than their saturated counterparts 2 and 4, and oxidation is easier for the silylenes 1 and 2 than for their germanium analogues. However the measured oxidation and reduction potentials do not correlate with the calculated I p's and E A's, probably due to kinetic and surface effects.

Original languageEnglish
Pages (from-to)5689-5693
Number of pages5
JournalOrganometallics
Volume23
Issue number24
DOIs
StatePublished - 22 Nov 2004

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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