Synthesis and reactivity of a (μ-1,1-hydroperoxo)(μ-hydroxo) dicopper(II) complex

Ligand hydroxylation by a bridging hydroperoxo ligand

Kyosuke Itoh, Hideki Hayashi, Hideki Furutachi, Takahiro Matsumoto, Shigenori Nagatomo, Takehiko Tosha, Shoichi Terada, Shuhei Fujinami, Masatatsu Suzuki, Teizo Kitagawa

Research output: Contribution to journalArticle

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Abstract

A new tetradentate tripodal ligand (L3) containing sterically bulky imidazolyl groups was synthesized, where L3 is tris(1-methyl-2-phenyl-4- imidazolylmethyl)amine. Reaction of a bis(μ-hydroxo)dicopper(II) complex, [Cu2(L3)2(OH)2]2+ (1), with H 2O2 in acetonitrile at -40 °C generated a (μ-1,1-hydroperoxo)dicopper(II) complex [Cu2(L3) 2(OOH)(OH)]2+ (2), which was characterized by various physicochemical measurements including X-ray crystallography. The crystal structure of 2 revealed that the complex cation has a Cu2(μ-1,1- OOH)(μ-OH) core and each copper has a square pyramidal structure having an N3O2 donor set with a weak ligation of a tertiary amine nitrogen in the apex. Consequently, one pendant arm of L3 in 2 is free from coordination, which produces a hydrophobic cavity around the Cu 2(μ-1,1-OOH)(μ-OH) core. The hydrophobic cavity is preserved by hydrogen bondings between the hydroperoxide and the imidazole nitrogen of an uncoordinated pendant arm in one side and the hydroxide and the imidazole nitrogen of an uncoordinated pendant arm in the other side. The hydrophobic cavity significantly suppresses the H/D and 16O/18O exchange reactions in 2 compared to that in 1 and stabilizes the Cu 2(μ-1,1-OOH)(μ-OH) core against decomposition. Decomposition of 2 in acetonitrile at 0 °C proceeded mainly via disproportionation of the hydroperoxo ligand and reduction of 2 to [Cu(L3)]+ by hydroperoxo ligand. In contrast, decomposition of a solid sample of 2 at 60 °C gave a complex having a hydroxylated ligand [Cu2(L3)(L3-OH)(OH) 2]2+ (2-(L3-OH)) as a main product, where L3-OH is an oxidized ligand in which one of the methylene groups of the pendant arms is hydroxylated. ESI-TOF/MS measurement showed that complex 2-(L3-OH) is stable in acetonitrile at -40 °C, whereas warming 2-(L3-OH) at room temperature resulted in the N-dealkylation from L3-OH to give an N-dealkylated ligand, bis(1-methyl-2-phenyl-4-imidazolylmethyl)amine (L2) in ∼80% yield based on 2, and 1-methyl-2-phenyl-4-formylimidazole (Phim-CHO). Isotope labeling experiments confirmed that the oxygen atom in both L3-OH and Phim-CHO come from OOH. This aliphatic hydroxylation performed by 2 is in marked contrast to the arene hydroxylation reported for some (μ-1,1-hydroperoxo)dicopper(II) complexes with a xylyl linker.

Original languageEnglish
Pages (from-to)5212-5223
Number of pages12
JournalJournal of the American Chemical Society
Volume127
Issue number14
DOIs
Publication statusPublished - Apr 13 2005
Externally publishedYes

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Hydroxylation
Ligands
Acetonitrile
Amines
Nitrogen
Decomposition
Dealkylation
Isotope Labeling
X ray crystallography
X Ray Crystallography
Hydrogen Bonding
Isotopes
Labeling
Hydrogen Peroxide
Ligation
Cations
Copper
Hydrogen bonds
Crystal structure
Positive ions

All Science Journal Classification (ASJC) codes

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

Cite this

Synthesis and reactivity of a (μ-1,1-hydroperoxo)(μ-hydroxo) dicopper(II) complex : Ligand hydroxylation by a bridging hydroperoxo ligand. / Itoh, Kyosuke; Hayashi, Hideki; Furutachi, Hideki; Matsumoto, Takahiro; Nagatomo, Shigenori; Tosha, Takehiko; Terada, Shoichi; Fujinami, Shuhei; Suzuki, Masatatsu; Kitagawa, Teizo.

In: Journal of the American Chemical Society, Vol. 127, No. 14, 13.04.2005, p. 5212-5223.

Research output: Contribution to journalArticle

Itoh, K, Hayashi, H, Furutachi, H, Matsumoto, T, Nagatomo, S, Tosha, T, Terada, S, Fujinami, S, Suzuki, M & Kitagawa, T 2005, 'Synthesis and reactivity of a (μ-1,1-hydroperoxo)(μ-hydroxo) dicopper(II) complex: Ligand hydroxylation by a bridging hydroperoxo ligand', Journal of the American Chemical Society, vol. 127, no. 14, pp. 5212-5223. https://doi.org/10.1021/ja047437h
Itoh, Kyosuke ; Hayashi, Hideki ; Furutachi, Hideki ; Matsumoto, Takahiro ; Nagatomo, Shigenori ; Tosha, Takehiko ; Terada, Shoichi ; Fujinami, Shuhei ; Suzuki, Masatatsu ; Kitagawa, Teizo. / Synthesis and reactivity of a (μ-1,1-hydroperoxo)(μ-hydroxo) dicopper(II) complex : Ligand hydroxylation by a bridging hydroperoxo ligand. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 14. pp. 5212-5223.
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abstract = "A new tetradentate tripodal ligand (L3) containing sterically bulky imidazolyl groups was synthesized, where L3 is tris(1-methyl-2-phenyl-4- imidazolylmethyl)amine. Reaction of a bis(μ-hydroxo)dicopper(II) complex, [Cu2(L3)2(OH)2]2+ (1), with H 2O2 in acetonitrile at -40 °C generated a (μ-1,1-hydroperoxo)dicopper(II) complex [Cu2(L3) 2(OOH)(OH)]2+ (2), which was characterized by various physicochemical measurements including X-ray crystallography. The crystal structure of 2 revealed that the complex cation has a Cu2(μ-1,1- OOH)(μ-OH) core and each copper has a square pyramidal structure having an N3O2 donor set with a weak ligation of a tertiary amine nitrogen in the apex. Consequently, one pendant arm of L3 in 2 is free from coordination, which produces a hydrophobic cavity around the Cu 2(μ-1,1-OOH)(μ-OH) core. The hydrophobic cavity is preserved by hydrogen bondings between the hydroperoxide and the imidazole nitrogen of an uncoordinated pendant arm in one side and the hydroxide and the imidazole nitrogen of an uncoordinated pendant arm in the other side. The hydrophobic cavity significantly suppresses the H/D and 16O/18O exchange reactions in 2 compared to that in 1 and stabilizes the Cu 2(μ-1,1-OOH)(μ-OH) core against decomposition. Decomposition of 2 in acetonitrile at 0 °C proceeded mainly via disproportionation of the hydroperoxo ligand and reduction of 2 to [Cu(L3)]+ by hydroperoxo ligand. In contrast, decomposition of a solid sample of 2 at 60 °C gave a complex having a hydroxylated ligand [Cu2(L3)(L3-OH)(OH) 2]2+ (2-(L3-OH)) as a main product, where L3-OH is an oxidized ligand in which one of the methylene groups of the pendant arms is hydroxylated. ESI-TOF/MS measurement showed that complex 2-(L3-OH) is stable in acetonitrile at -40 °C, whereas warming 2-(L3-OH) at room temperature resulted in the N-dealkylation from L3-OH to give an N-dealkylated ligand, bis(1-methyl-2-phenyl-4-imidazolylmethyl)amine (L2) in ∼80{\%} yield based on 2, and 1-methyl-2-phenyl-4-formylimidazole (Phim-CHO). Isotope labeling experiments confirmed that the oxygen atom in both L3-OH and Phim-CHO come from OOH. This aliphatic hydroxylation performed by 2 is in marked contrast to the arene hydroxylation reported for some (μ-1,1-hydroperoxo)dicopper(II) complexes with a xylyl linker.",
author = "Kyosuke Itoh and Hideki Hayashi and Hideki Furutachi and Takahiro Matsumoto and Shigenori Nagatomo and Takehiko Tosha and Shoichi Terada and Shuhei Fujinami and Masatatsu Suzuki and Teizo Kitagawa",
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TY - JOUR

T1 - Synthesis and reactivity of a (μ-1,1-hydroperoxo)(μ-hydroxo) dicopper(II) complex

T2 - Ligand hydroxylation by a bridging hydroperoxo ligand

AU - Itoh, Kyosuke

AU - Hayashi, Hideki

AU - Furutachi, Hideki

AU - Matsumoto, Takahiro

AU - Nagatomo, Shigenori

AU - Tosha, Takehiko

AU - Terada, Shoichi

AU - Fujinami, Shuhei

AU - Suzuki, Masatatsu

AU - Kitagawa, Teizo

PY - 2005/4/13

Y1 - 2005/4/13

N2 - A new tetradentate tripodal ligand (L3) containing sterically bulky imidazolyl groups was synthesized, where L3 is tris(1-methyl-2-phenyl-4- imidazolylmethyl)amine. Reaction of a bis(μ-hydroxo)dicopper(II) complex, [Cu2(L3)2(OH)2]2+ (1), with H 2O2 in acetonitrile at -40 °C generated a (μ-1,1-hydroperoxo)dicopper(II) complex [Cu2(L3) 2(OOH)(OH)]2+ (2), which was characterized by various physicochemical measurements including X-ray crystallography. The crystal structure of 2 revealed that the complex cation has a Cu2(μ-1,1- OOH)(μ-OH) core and each copper has a square pyramidal structure having an N3O2 donor set with a weak ligation of a tertiary amine nitrogen in the apex. Consequently, one pendant arm of L3 in 2 is free from coordination, which produces a hydrophobic cavity around the Cu 2(μ-1,1-OOH)(μ-OH) core. The hydrophobic cavity is preserved by hydrogen bondings between the hydroperoxide and the imidazole nitrogen of an uncoordinated pendant arm in one side and the hydroxide and the imidazole nitrogen of an uncoordinated pendant arm in the other side. The hydrophobic cavity significantly suppresses the H/D and 16O/18O exchange reactions in 2 compared to that in 1 and stabilizes the Cu 2(μ-1,1-OOH)(μ-OH) core against decomposition. Decomposition of 2 in acetonitrile at 0 °C proceeded mainly via disproportionation of the hydroperoxo ligand and reduction of 2 to [Cu(L3)]+ by hydroperoxo ligand. In contrast, decomposition of a solid sample of 2 at 60 °C gave a complex having a hydroxylated ligand [Cu2(L3)(L3-OH)(OH) 2]2+ (2-(L3-OH)) as a main product, where L3-OH is an oxidized ligand in which one of the methylene groups of the pendant arms is hydroxylated. ESI-TOF/MS measurement showed that complex 2-(L3-OH) is stable in acetonitrile at -40 °C, whereas warming 2-(L3-OH) at room temperature resulted in the N-dealkylation from L3-OH to give an N-dealkylated ligand, bis(1-methyl-2-phenyl-4-imidazolylmethyl)amine (L2) in ∼80% yield based on 2, and 1-methyl-2-phenyl-4-formylimidazole (Phim-CHO). Isotope labeling experiments confirmed that the oxygen atom in both L3-OH and Phim-CHO come from OOH. This aliphatic hydroxylation performed by 2 is in marked contrast to the arene hydroxylation reported for some (μ-1,1-hydroperoxo)dicopper(II) complexes with a xylyl linker.

AB - A new tetradentate tripodal ligand (L3) containing sterically bulky imidazolyl groups was synthesized, where L3 is tris(1-methyl-2-phenyl-4- imidazolylmethyl)amine. Reaction of a bis(μ-hydroxo)dicopper(II) complex, [Cu2(L3)2(OH)2]2+ (1), with H 2O2 in acetonitrile at -40 °C generated a (μ-1,1-hydroperoxo)dicopper(II) complex [Cu2(L3) 2(OOH)(OH)]2+ (2), which was characterized by various physicochemical measurements including X-ray crystallography. The crystal structure of 2 revealed that the complex cation has a Cu2(μ-1,1- OOH)(μ-OH) core and each copper has a square pyramidal structure having an N3O2 donor set with a weak ligation of a tertiary amine nitrogen in the apex. Consequently, one pendant arm of L3 in 2 is free from coordination, which produces a hydrophobic cavity around the Cu 2(μ-1,1-OOH)(μ-OH) core. The hydrophobic cavity is preserved by hydrogen bondings between the hydroperoxide and the imidazole nitrogen of an uncoordinated pendant arm in one side and the hydroxide and the imidazole nitrogen of an uncoordinated pendant arm in the other side. The hydrophobic cavity significantly suppresses the H/D and 16O/18O exchange reactions in 2 compared to that in 1 and stabilizes the Cu 2(μ-1,1-OOH)(μ-OH) core against decomposition. Decomposition of 2 in acetonitrile at 0 °C proceeded mainly via disproportionation of the hydroperoxo ligand and reduction of 2 to [Cu(L3)]+ by hydroperoxo ligand. In contrast, decomposition of a solid sample of 2 at 60 °C gave a complex having a hydroxylated ligand [Cu2(L3)(L3-OH)(OH) 2]2+ (2-(L3-OH)) as a main product, where L3-OH is an oxidized ligand in which one of the methylene groups of the pendant arms is hydroxylated. ESI-TOF/MS measurement showed that complex 2-(L3-OH) is stable in acetonitrile at -40 °C, whereas warming 2-(L3-OH) at room temperature resulted in the N-dealkylation from L3-OH to give an N-dealkylated ligand, bis(1-methyl-2-phenyl-4-imidazolylmethyl)amine (L2) in ∼80% yield based on 2, and 1-methyl-2-phenyl-4-formylimidazole (Phim-CHO). Isotope labeling experiments confirmed that the oxygen atom in both L3-OH and Phim-CHO come from OOH. This aliphatic hydroxylation performed by 2 is in marked contrast to the arene hydroxylation reported for some (μ-1,1-hydroperoxo)dicopper(II) complexes with a xylyl linker.

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