Chemical basis for high activity in oxygenation of cyclohexane catalyzed by dinuclear iron(III) complexes with ethereal oxygen containing ligand and hydrogen peroxide system

Sayo Ito, Takashi Okuno, Hiroki Itoh, Shigeru Ohba, Hideaki Matsushima, Tadashi Tokii, Yuzo Nishida

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Abstract

The crystal structures of two binuclear iron(III) complexes with linear μ-oxo bridge, Fe2OCl2(tfpy)2(ClO4) 2·2 CH3CN and Fe2OCl2(epy)2(ClO4)2 were determined, where (tfpy) and (epy) represent N,N-bis(2-pyridylmethyl)-tetrahydrofurfurylamine and N,N-bis(2-pyridylmethyl)-2-ethoxyethylamine, respectively. Their structural features are essentially the same as that of the corresponding linear binuclear complex with (tpa)-complex, Fe2OCl2-(tpa)2(ClO4)2, where (tpa) is tris(2-pyridylmethyl)amine; the ligands (tipy) and (epy) act as a tetradentate tripod-like ligand, and Fe-O (ethereal oxygen atom; these are located at the trans-position of bridging oxo-oxygen atom) distances are 2.209(4) and 2.264(2) Å for (tfpy) and (epy) compounds, respectively. These two (tfpy) and (epy) complexes exhibited much higher activity for the oxygenation of cyclohexane in the presence of hydrogen peroxide than that of the (tpa) complex. In contrast to this, the former two complexes exhibit negligible activity for the decomposition of hydrogen peroxide, whereas the catalase-like function of the (tpa) compound is remarkable. These are indicating that an active species for oxygenation of cyclohexane, which is assumed to be an iron(III)-hydroperoxide adduct with η1-coordination mode, should be different from that is operating for decomposition of hydrogen peroxide; for the latter case formation of a (μ-η11-peroxo)diiron(III) species being stressed. The EHMO calculation showed that electronic interaction between the monodentate hydroperoxide adduct of the binuclear iron(III)-(tfpy) compound and the tetrahydrofuran ring of the ligand system may lead to facile peroxide-tetrahydrofuran linkage formation, and the interaction described above should promote the O-O cleavage of the peroxide ion heterolytically. Based on these discussions, it was concluded that heterolytic O-O bond cleavage of the iron(III)-hydroperoxide adduct caused by electronic interaction with organic moiety containing an ethereal-oxygen and by approach of the substrate which donates electron to the peroxide adduct should play an important role in producing a high-valent iron-oxo species in these systems. In the case of (tpa) complex, formation of a hydroperoxide adduct linking with the ligand system seems to be unfavorable because of both the steric and electronic reasons.

Original languageEnglish
Pages (from-to)719-727
Number of pages9
JournalZeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
Volume52
Issue number6
Publication statusPublished - 1997 Jun

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Oxygenation
Hydrogen Peroxide
Iron
Oxygen
Ligands
Peroxides
Iron compounds
Decomposition
Atoms
Cyclohexane
Catalase
Crystal structure
Ions
Electrons
Substrates
perchlorate

Keywords

  • Binuclear Iron(III) Complexes
  • Cyclohexane
  • Ethereal Oxygen

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Chemical basis for high activity in oxygenation of cyclohexane catalyzed by dinuclear iron(III) complexes with ethereal oxygen containing ligand and hydrogen peroxide system. / Ito, Sayo; Okuno, Takashi; Itoh, Hiroki; Ohba, Shigeru; Matsushima, Hideaki; Tokii, Tadashi; Nishida, Yuzo.

In: Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, Vol. 52, No. 6, 06.1997, p. 719-727.

Research output: Contribution to journalArticle

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abstract = "The crystal structures of two binuclear iron(III) complexes with linear μ-oxo bridge, Fe2OCl2(tfpy)2(ClO4) 2·2 CH3CN and Fe2OCl2(epy)2(ClO4)2 were determined, where (tfpy) and (epy) represent N,N-bis(2-pyridylmethyl)-tetrahydrofurfurylamine and N,N-bis(2-pyridylmethyl)-2-ethoxyethylamine, respectively. Their structural features are essentially the same as that of the corresponding linear binuclear complex with (tpa)-complex, Fe2OCl2-(tpa)2(ClO4)2, where (tpa) is tris(2-pyridylmethyl)amine; the ligands (tipy) and (epy) act as a tetradentate tripod-like ligand, and Fe-O (ethereal oxygen atom; these are located at the trans-position of bridging oxo-oxygen atom) distances are 2.209(4) and 2.264(2) {\AA} for (tfpy) and (epy) compounds, respectively. These two (tfpy) and (epy) complexes exhibited much higher activity for the oxygenation of cyclohexane in the presence of hydrogen peroxide than that of the (tpa) complex. In contrast to this, the former two complexes exhibit negligible activity for the decomposition of hydrogen peroxide, whereas the catalase-like function of the (tpa) compound is remarkable. These are indicating that an active species for oxygenation of cyclohexane, which is assumed to be an iron(III)-hydroperoxide adduct with η1-coordination mode, should be different from that is operating for decomposition of hydrogen peroxide; for the latter case formation of a (μ-η1:η1-peroxo)diiron(III) species being stressed. The EHMO calculation showed that electronic interaction between the monodentate hydroperoxide adduct of the binuclear iron(III)-(tfpy) compound and the tetrahydrofuran ring of the ligand system may lead to facile peroxide-tetrahydrofuran linkage formation, and the interaction described above should promote the O-O cleavage of the peroxide ion heterolytically. Based on these discussions, it was concluded that heterolytic O-O bond cleavage of the iron(III)-hydroperoxide adduct caused by electronic interaction with organic moiety containing an ethereal-oxygen and by approach of the substrate which donates electron to the peroxide adduct should play an important role in producing a high-valent iron-oxo species in these systems. In the case of (tpa) complex, formation of a hydroperoxide adduct linking with the ligand system seems to be unfavorable because of both the steric and electronic reasons.",
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T1 - Chemical basis for high activity in oxygenation of cyclohexane catalyzed by dinuclear iron(III) complexes with ethereal oxygen containing ligand and hydrogen peroxide system

AU - Ito, Sayo

AU - Okuno, Takashi

AU - Itoh, Hiroki

AU - Ohba, Shigeru

AU - Matsushima, Hideaki

AU - Tokii, Tadashi

AU - Nishida, Yuzo

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N2 - The crystal structures of two binuclear iron(III) complexes with linear μ-oxo bridge, Fe2OCl2(tfpy)2(ClO4) 2·2 CH3CN and Fe2OCl2(epy)2(ClO4)2 were determined, where (tfpy) and (epy) represent N,N-bis(2-pyridylmethyl)-tetrahydrofurfurylamine and N,N-bis(2-pyridylmethyl)-2-ethoxyethylamine, respectively. Their structural features are essentially the same as that of the corresponding linear binuclear complex with (tpa)-complex, Fe2OCl2-(tpa)2(ClO4)2, where (tpa) is tris(2-pyridylmethyl)amine; the ligands (tipy) and (epy) act as a tetradentate tripod-like ligand, and Fe-O (ethereal oxygen atom; these are located at the trans-position of bridging oxo-oxygen atom) distances are 2.209(4) and 2.264(2) Å for (tfpy) and (epy) compounds, respectively. These two (tfpy) and (epy) complexes exhibited much higher activity for the oxygenation of cyclohexane in the presence of hydrogen peroxide than that of the (tpa) complex. In contrast to this, the former two complexes exhibit negligible activity for the decomposition of hydrogen peroxide, whereas the catalase-like function of the (tpa) compound is remarkable. These are indicating that an active species for oxygenation of cyclohexane, which is assumed to be an iron(III)-hydroperoxide adduct with η1-coordination mode, should be different from that is operating for decomposition of hydrogen peroxide; for the latter case formation of a (μ-η1:η1-peroxo)diiron(III) species being stressed. The EHMO calculation showed that electronic interaction between the monodentate hydroperoxide adduct of the binuclear iron(III)-(tfpy) compound and the tetrahydrofuran ring of the ligand system may lead to facile peroxide-tetrahydrofuran linkage formation, and the interaction described above should promote the O-O cleavage of the peroxide ion heterolytically. Based on these discussions, it was concluded that heterolytic O-O bond cleavage of the iron(III)-hydroperoxide adduct caused by electronic interaction with organic moiety containing an ethereal-oxygen and by approach of the substrate which donates electron to the peroxide adduct should play an important role in producing a high-valent iron-oxo species in these systems. In the case of (tpa) complex, formation of a hydroperoxide adduct linking with the ligand system seems to be unfavorable because of both the steric and electronic reasons.

AB - The crystal structures of two binuclear iron(III) complexes with linear μ-oxo bridge, Fe2OCl2(tfpy)2(ClO4) 2·2 CH3CN and Fe2OCl2(epy)2(ClO4)2 were determined, where (tfpy) and (epy) represent N,N-bis(2-pyridylmethyl)-tetrahydrofurfurylamine and N,N-bis(2-pyridylmethyl)-2-ethoxyethylamine, respectively. Their structural features are essentially the same as that of the corresponding linear binuclear complex with (tpa)-complex, Fe2OCl2-(tpa)2(ClO4)2, where (tpa) is tris(2-pyridylmethyl)amine; the ligands (tipy) and (epy) act as a tetradentate tripod-like ligand, and Fe-O (ethereal oxygen atom; these are located at the trans-position of bridging oxo-oxygen atom) distances are 2.209(4) and 2.264(2) Å for (tfpy) and (epy) compounds, respectively. These two (tfpy) and (epy) complexes exhibited much higher activity for the oxygenation of cyclohexane in the presence of hydrogen peroxide than that of the (tpa) complex. In contrast to this, the former two complexes exhibit negligible activity for the decomposition of hydrogen peroxide, whereas the catalase-like function of the (tpa) compound is remarkable. These are indicating that an active species for oxygenation of cyclohexane, which is assumed to be an iron(III)-hydroperoxide adduct with η1-coordination mode, should be different from that is operating for decomposition of hydrogen peroxide; for the latter case formation of a (μ-η1:η1-peroxo)diiron(III) species being stressed. The EHMO calculation showed that electronic interaction between the monodentate hydroperoxide adduct of the binuclear iron(III)-(tfpy) compound and the tetrahydrofuran ring of the ligand system may lead to facile peroxide-tetrahydrofuran linkage formation, and the interaction described above should promote the O-O cleavage of the peroxide ion heterolytically. Based on these discussions, it was concluded that heterolytic O-O bond cleavage of the iron(III)-hydroperoxide adduct caused by electronic interaction with organic moiety containing an ethereal-oxygen and by approach of the substrate which donates electron to the peroxide adduct should play an important role in producing a high-valent iron-oxo species in these systems. In the case of (tpa) complex, formation of a hydroperoxide adduct linking with the ligand system seems to be unfavorable because of both the steric and electronic reasons.

KW - Binuclear Iron(III) Complexes

KW - Cyclohexane

KW - Ethereal Oxygen

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