Activation of molecular oxygen by a dioxygenase pathway by a ruthenium bis-bipyridine compound with a proximal selenium site

Alexander Laskavy, Linda J W Shimon, Leonid Konstantinovski, Mark A. Iron, Ronny Neumann

Research output: Contribution to journalArticle

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Abstract

A ruthenium(II) bipyridine complex with proximal phenylselenium tethers, [Ru](H2O)2, reacted intramolecularly with O2 in a protic slightly acidic solvent, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), to yield an O-O bond cleaved product, [Ru](O)2, with formation of two Ru-O-Se moieties. This stable compound was isolated, and its structure was determined by X-ray diffraction. The identification of the compound in solution was confirmed by ESI-MS and the 1H NMR with the associated Curie plot that showed that [Ru](O)2 was paramagnetic. The magnetic susceptibility was 2.8 μB by Evan's method suggesting a ground state triplet or biradical. DFT calculations, however, predicted a ground state singlet and an oxidized Se atom. Further it was shown that [Ru](O)2 is a potent oxygen transfer species of both O2-derived atoms to triphenylphosphine and a nucleophilic alkene such as 2,3-dimethyl-2-butene in both HFIP and acetonitrile. UV-vis spectroscopy combined with the measured stoichiometry of PPh3:O2 = ̃2 in a catalytic oxidation of PPh3 suggests a dioxygenase type activation of O 2 with structural identification of the O-O bond cleavage reaction step, formation of [Ru](O)2 as an intermediate, and the proof that [Ru](O)2 is a donor of both oxygen atoms.

Original languageEnglish
Pages (from-to)517-523
Number of pages7
JournalJournal of the American Chemical Society
Volume132
Issue number2
DOIs
Publication statusPublished - Jan 20 2010

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Dioxygenases
Molecular oxygen
Selenium
Ruthenium
Chemical activation
Oxygen
Atoms
Ground state
Alkenes
X-Ray Diffraction
Spectrum Analysis
Catalytic oxidation
Propanol
Ultraviolet spectroscopy
Acetonitrile
Magnetic susceptibility
Butenes
Discrete Fourier transforms
Stoichiometry
Olefins

ASJC Scopus subject areas

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

Cite this

Activation of molecular oxygen by a dioxygenase pathway by a ruthenium bis-bipyridine compound with a proximal selenium site. / Laskavy, Alexander; Shimon, Linda J W; Konstantinovski, Leonid; Iron, Mark A.; Neumann, Ronny.

In: Journal of the American Chemical Society, Vol. 132, No. 2, 20.01.2010, p. 517-523.

Research output: Contribution to journalArticle

Laskavy, Alexander ; Shimon, Linda J W ; Konstantinovski, Leonid ; Iron, Mark A. ; Neumann, Ronny. / Activation of molecular oxygen by a dioxygenase pathway by a ruthenium bis-bipyridine compound with a proximal selenium site. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 2. pp. 517-523.
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