Roles of carboxylate donors in O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) with a new carboxylate-containing dinucleating ligand

Masahito Kodera, Tomokazu Tsuji, Tomohiro Yasunaga, Yuka Kawahara, Tomoya Hirano, Yutaka Hitomi, Takashi Nomura, Takashi Ogura, Yoshio Kobayashi, P. K. Sajith, Yoshihito Shiota, Kazunari Yoshizawa

研究成果: ジャーナルへの寄稿記事

9 引用 (Scopus)

抄録

Dioxygen activation proceeds via O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) in soluble methane mono-oxygenase (sMMO). Recently, we have shown that reversible O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) is attained with a bis-tpa type dinucleating ligand, 6-hpa. In this study, a new carboxylate-containing dinucleating ligand, 1,2-bis[2-(N-2-pyridylmethyl-N-glycinylmethyl)-6-pyridyl]ethane (H 2BPG2E) and its μ-oxodiaquadi-iron(iii) complexes [Fe2(μ-O)(H2O)2(BPG2E)]X 2 [X = ClO4 (2a) or OTf (2b)] were synthesized to mimic a common carboxylate-rich coordination environment in O2-activating non-heme di-iron enzymes including sMMO. The crystal structures of 2a and 2b revealed that BPG2E prefers a syn-diaqua binding mode. 2b catalyzed the epoxidation of alkenes with H2O2. A new purple species was formed upon reaction of 2b with H2O2, and characterized by the elemental analysis and spectral and kinetic studies. These clearly showed that the purple species was a μ-oxo-μ-peroxodi-iron(iii), and converted to high-spin μ-oxodioxodi-iron(iv) via rate-determining reversible O-O bond scission. In comparison of BPG2E with 6-hpa, it is shown that the carboxylate donor stabilizes the Fe-O-O-Fe structure of the peroxo complex due to the structural effect to retard O-O bond scission. This may shed light on the roles of carboxylate donors in the dioxygen activation of non-heme di-iron enzymes. This journal is

元の言語英語
ページ(範囲)2282-2292
ページ数11
ジャーナルChemical Science
5
発行部数6
DOI
出版物ステータス出版済み - 1 1 2014

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Iron
Ligands
Oxygenases
Methane
Chemical activation
Oxygen
Ethane
Epoxidation
Alkenes
Enzymes
Crystal structure
Kinetics
Chemical analysis

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

これを引用

Roles of carboxylate donors in O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) with a new carboxylate-containing dinucleating ligand. / Kodera, Masahito; Tsuji, Tomokazu; Yasunaga, Tomohiro; Kawahara, Yuka; Hirano, Tomoya; Hitomi, Yutaka; Nomura, Takashi; Ogura, Takashi; Kobayashi, Yoshio; Sajith, P. K.; Shiota, Yoshihito; Yoshizawa, Kazunari.

:: Chemical Science, 巻 5, 番号 6, 01.01.2014, p. 2282-2292.

研究成果: ジャーナルへの寄稿記事

Kodera, M, Tsuji, T, Yasunaga, T, Kawahara, Y, Hirano, T, Hitomi, Y, Nomura, T, Ogura, T, Kobayashi, Y, Sajith, PK, Shiota, Y & Yoshizawa, K 2014, 'Roles of carboxylate donors in O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) with a new carboxylate-containing dinucleating ligand', Chemical Science, 巻. 5, 番号 6, pp. 2282-2292. https://doi.org/10.1039/c3sc51541a
Kodera, Masahito ; Tsuji, Tomokazu ; Yasunaga, Tomohiro ; Kawahara, Yuka ; Hirano, Tomoya ; Hitomi, Yutaka ; Nomura, Takashi ; Ogura, Takashi ; Kobayashi, Yoshio ; Sajith, P. K. ; Shiota, Yoshihito ; Yoshizawa, Kazunari. / Roles of carboxylate donors in O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) with a new carboxylate-containing dinucleating ligand. :: Chemical Science. 2014 ; 巻 5, 番号 6. pp. 2282-2292.
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abstract = "Dioxygen activation proceeds via O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) in soluble methane mono-oxygenase (sMMO). Recently, we have shown that reversible O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) is attained with a bis-tpa type dinucleating ligand, 6-hpa. In this study, a new carboxylate-containing dinucleating ligand, 1,2-bis[2-(N-2-pyridylmethyl-N-glycinylmethyl)-6-pyridyl]ethane (H 2BPG2E) and its μ-oxodiaquadi-iron(iii) complexes [Fe2(μ-O)(H2O)2(BPG2E)]X 2 [X = ClO4 (2a) or OTf (2b)] were synthesized to mimic a common carboxylate-rich coordination environment in O2-activating non-heme di-iron enzymes including sMMO. The crystal structures of 2a and 2b revealed that BPG2E prefers a syn-diaqua binding mode. 2b catalyzed the epoxidation of alkenes with H2O2. A new purple species was formed upon reaction of 2b with H2O2, and characterized by the elemental analysis and spectral and kinetic studies. These clearly showed that the purple species was a μ-oxo-μ-peroxodi-iron(iii), and converted to high-spin μ-oxodioxodi-iron(iv) via rate-determining reversible O-O bond scission. In comparison of BPG2E with 6-hpa, it is shown that the carboxylate donor stabilizes the Fe-O-O-Fe structure of the peroxo complex due to the structural effect to retard O-O bond scission. This may shed light on the roles of carboxylate donors in the dioxygen activation of non-heme di-iron enzymes. This journal is",
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AU - Kodera, Masahito

AU - Tsuji, Tomokazu

AU - Yasunaga, Tomohiro

AU - Kawahara, Yuka

AU - Hirano, Tomoya

AU - Hitomi, Yutaka

AU - Nomura, Takashi

AU - Ogura, Takashi

AU - Kobayashi, Yoshio

AU - Sajith, P. K.

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

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N2 - Dioxygen activation proceeds via O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) in soluble methane mono-oxygenase (sMMO). Recently, we have shown that reversible O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) is attained with a bis-tpa type dinucleating ligand, 6-hpa. In this study, a new carboxylate-containing dinucleating ligand, 1,2-bis[2-(N-2-pyridylmethyl-N-glycinylmethyl)-6-pyridyl]ethane (H 2BPG2E) and its μ-oxodiaquadi-iron(iii) complexes [Fe2(μ-O)(H2O)2(BPG2E)]X 2 [X = ClO4 (2a) or OTf (2b)] were synthesized to mimic a common carboxylate-rich coordination environment in O2-activating non-heme di-iron enzymes including sMMO. The crystal structures of 2a and 2b revealed that BPG2E prefers a syn-diaqua binding mode. 2b catalyzed the epoxidation of alkenes with H2O2. A new purple species was formed upon reaction of 2b with H2O2, and characterized by the elemental analysis and spectral and kinetic studies. These clearly showed that the purple species was a μ-oxo-μ-peroxodi-iron(iii), and converted to high-spin μ-oxodioxodi-iron(iv) via rate-determining reversible O-O bond scission. In comparison of BPG2E with 6-hpa, it is shown that the carboxylate donor stabilizes the Fe-O-O-Fe structure of the peroxo complex due to the structural effect to retard O-O bond scission. This may shed light on the roles of carboxylate donors in the dioxygen activation of non-heme di-iron enzymes. This journal is

AB - Dioxygen activation proceeds via O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) in soluble methane mono-oxygenase (sMMO). Recently, we have shown that reversible O-O bond scission of peroxodi-iron(iii) to high-spin oxodi-iron(iv) is attained with a bis-tpa type dinucleating ligand, 6-hpa. In this study, a new carboxylate-containing dinucleating ligand, 1,2-bis[2-(N-2-pyridylmethyl-N-glycinylmethyl)-6-pyridyl]ethane (H 2BPG2E) and its μ-oxodiaquadi-iron(iii) complexes [Fe2(μ-O)(H2O)2(BPG2E)]X 2 [X = ClO4 (2a) or OTf (2b)] were synthesized to mimic a common carboxylate-rich coordination environment in O2-activating non-heme di-iron enzymes including sMMO. The crystal structures of 2a and 2b revealed that BPG2E prefers a syn-diaqua binding mode. 2b catalyzed the epoxidation of alkenes with H2O2. A new purple species was formed upon reaction of 2b with H2O2, and characterized by the elemental analysis and spectral and kinetic studies. These clearly showed that the purple species was a μ-oxo-μ-peroxodi-iron(iii), and converted to high-spin μ-oxodioxodi-iron(iv) via rate-determining reversible O-O bond scission. In comparison of BPG2E with 6-hpa, it is shown that the carboxylate donor stabilizes the Fe-O-O-Fe structure of the peroxo complex due to the structural effect to retard O-O bond scission. This may shed light on the roles of carboxylate donors in the dioxygen activation of non-heme di-iron enzymes. This journal is

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