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

doi:10.1021/ja9047027

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^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

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 language	English
Pages (from-to)	517-523
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	132
Issue number	2
DOIs	https://doi.org/10.1021/ja9047027
State	Published - 20 Jan 2010
Externally published	Yes

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

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.",

author = "Alexander Laskavy and Shimon, \{Linda J.W.\} and Leonid Konstantinovski and Iron, \{Mark A.\} and Ronny Neumann",

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T1 - Activation of molecular oxygen by a dioxygenase pathway by a ruthenium bis-bipyridine compound with a proximal selenium site

AU - Laskavy, Alexander

AU - Shimon, Linda J.W.

AU - Konstantinovski, Leonid

AU - Iron, Mark A.

AU - Neumann, Ronny

PY - 2010/1/20

Y1 - 2010/1/20

N2 - 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.

AB - 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.

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ER -

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

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