Long-Range Intervalence Electron Tunneling through Fully Saturated Systems

C. A. Stein, Nita A. Lewis, Gunther Seitz

Research output: Contribution to journalArticle

132 Scopus citations

Abstract

The compounds (μ-2,8-dithiadispiro[3.1.3.1]decane)-decaamminediruthenium(II,II) hexafluorophosphate, [(N-H3)5RuS2C8H 12Ru(NH3)5](PF6)4, and (μ-2,10-dithiatrispiro[3.1.1.3.1.1]tridecane)-decaamminediruthenium(II,II) hexafluorophosphate, [(NH3)5RuS2C11H 16Ru(NH3)5](PF6)4, were prepared, and upon oxidation, their intervalence properties were measured. The spiro binuclear with three rings had an IT band at 808 nm (∈ 9 ± 1 M-1 cm-1) and that with four rings had an IT band at 690 nm (∈ 2.3 ± 0.7 M-1 cm-1). This compares with a band at 910 nm (∈ 43 ± 2) measured earlier for the two-ring spiro binuclear. The through-bond distances between ruthenium centers range from 11.3 to 17.5 Å. The values of the electron tunneling matrix elements were calculated from Hopfield's theory and were found to be 1.7 × 10-2, 6.8 × 10-3, and 3.1 × 10-3 eV for the two-ring, three-ring, and four-ring binuclears, respectively. These correspond to rate constants of 8.0 × 107, 4.9 × 106, and 3.5 × 104 s-1, respectively, for the three binuclears. The results are discussed in terms of long-range tunneling and are compared to results obtained in solid matrices and biological systems.

Original languageEnglish (US)
Pages (from-to)2596-2599
Number of pages4
JournalJournal of the American Chemical Society
Volume104
Issue number9
DOIs
StatePublished - Jan 1 1982
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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