Through-space interaction mediated by a sulfoxide

G. Joel Meyer, Elliott R. Smith, Takahiro Sakamoto, Dennis L. Lichtenberger, Richard S. Glass

Research output: Research - peer-reviewArticle

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Abstract

Two new bisferrocenylphenylsulfoxides were synthesized and studied to determine the effect of the polar sulfoxide bond on through-space interaction between ferrocene moieties. The electronic and redox properties of these compounds were studied by ultraviolet (UV) photoelectron spectroscopy, cyclic voltammetry, differential pulse voltammetry, and density functional theory computations. Electrochemical results for 2,6-bis(ferrocenyl) thioanisole S-oxide 5b show two, fully reversible one-electron redox processes. The initial oxidation shows a 62-mV negative shift compared with the sulfide analog 2,6-bis(ferrocenyl)thioanisole, and an increased peak separation for the oxidation of 160 versus 145 mV. No peak separation is observed in 6b. No intervalence charge transfer band was observed in the complex 5b<sup>+1</sup> by UV-Visible/Near-Infrared spectroscopy, ruling out electronic communication. Thus, the through-space electrostatic interactions of the sulfoxide renders the non-equivalent ferrocenes in 5b to have different oxidation potentials.

LanguageEnglish (US)
Pages1242-1246
Number of pages5
JournalPhosphorus, Sulfur and Silicon and Related Elements
Volume190
Issue number8
DOIs
StatePublished - Aug 3 2015

Fingerprint

sulfoxide
Oxidation
Oxidation-Reduction
methylphenylsulfide
Photoelectron Spectroscopy
Near-Infrared Spectroscopy
Sulfides
Static Electricity
Oxides
Electrons
ferrocene
Ultraviolet photoelectron spectroscopy
Near infrared spectroscopy
Coulomb interactions
Density functional theory
Charge transfer
Communication

Keywords

  • electrostatic interaction
  • Ferrocene
  • mixed valence

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Biochemistry

Cite this

Through-space interaction mediated by a sulfoxide. / Joel Meyer, G.; Smith, Elliott R.; Sakamoto, Takahiro; Lichtenberger, Dennis L.; Glass, Richard S.

In: Phosphorus, Sulfur and Silicon and Related Elements, Vol. 190, No. 8, 03.08.2015, p. 1242-1246.

Research output: Research - peer-reviewArticle

Joel Meyer, G. ; Smith, Elliott R. ; Sakamoto, Takahiro ; Lichtenberger, Dennis L. ; Glass, Richard S./ Through-space interaction mediated by a sulfoxide. In: Phosphorus, Sulfur and Silicon and Related Elements. 2015 ; Vol. 190, No. 8. pp. 1242-1246
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