Synthesis, Structure, and Greatly Improved Reversible O2 Binding in a Structurally Modulated μ‐η2:η2‐Peroxodicopper(<scp>II</scp>) Complex with Room‐Temperature Stability

Kodera, Masahito; Kajita, Yuuji; Tachi, Yoshimitsu; Katayama, Kou; Kawasaki, Koji; Hirota, Shun; Fujinami, Shuhei; Suzuki, Masatatsu

doi:10.1002/anie.200352737

Cited by 67 publications

(37 citation statements)

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“…[6] Dicopper biosites are known to catalyze oxidations of various hydrocarbons,s uch as aromatic compounds and alkanes. [7] Va rious dicopper complexes have been developed for O 2 binding, [8] but are less studied as catalysts for the oxidation of methane and benzene. [9] Herein, it was found that ad icopper complex with the dinucleating ligand 1,2bis[2-[bis(2-pyridylmethyl)aminomethyl]-6-pyridyl]ethane [10] (6-hpa), [Cu 2 (m-OH)(6-hpa)](ClO 4 ) 3 (1), exhibits high catalytic activity in selective hydroxylation of benzene with H 2 O 2 .…”

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Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide

et al. 2017

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A dicopper(II) complex, stabilized by the bis(tpa) ligand 1,2-bis[2-[bis(2-pyridylmethyl)aminomethyl]-6-pyridyl]ethane (6-hpa), [Cu (μ-OH)(6-hpa)] , was synthesized and structurally characterized. This complex catalyzed selective hydroxylation of benzene to phenol using H O , thus attaining large turnover numbers (TONs) and high H O efficiency. The TON after 40 hours for the phenol production exceeded 12000 in MeCN at 50 °C under N , the highest value reported for benzene hydroxylation with H O catalyzed by homogeneous complexes. At 22 % benzene conversion, phenol (95.2 %) and p-benzoquinone (4.8 %) were produced. The mechanism of H O activation and benzene hydroxylation is proposed.

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Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide

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“…The 29 Si and 13 C CPMAS NMR spectra for M1 are presented in Figure S2 in the Supporting Information. Materials M1 and M2 were formed with a high degree of polycondensation, as the 29 Si NMR spectrum displayed mainly T 3 and Q 4 substructures.…”

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confidence: 99%

“…Materials M1 and M2 were formed with a high degree of polycondensation, as the 29 Si NMR spectrum displayed mainly T 3 and Q 4 substructures. The T n signals are indicative of the incorporation and high condensation of the organosilane derivative within the inorganic silica.…”

Section: Structural and Textural Characterizationmentioning

confidence: 99%

“…[25] Although these two latter oxygenated species are the most stable described to date, there is a paucity of examples of biomimetic models capable of coordinating molecular oxygen reversibly at room temperature. [26][27][28][29] Warming oxygenated species generally causes their decomposition to Cu II complexes through processes involving oxidation or ligand dealkylation. [13,30,31] Hence, most of them were only stable for a few minutes or a few hours, and their regeneration was not possible more than once.…”

Section: Introductionmentioning

confidence: 99%

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Reversible Coordination of Dioxygen by Tripodal Tetraamine Copper Complexes Incorporated in a Porous Silica Framework

Suspène

Brandès

Guilard

2010

Chemistry A European J

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The present study reports the synthesis and rational design of porous structured materials by using a templating method. A tetraethoxysilylated tripodal tetraamine (TREN) was covalently incorporated in a silica framework with a double imprint: A surfactant template and a metal ion imprint. The presence of a cationic surfactant (CTAB) endowed the material with a high porosity, and the tripodal or square-pyramidal topology of the ligand was preserved thanks to the use of the silylated Cu(II) complex. After removal of the surfactant and de-metalation, the incorporated tetraamine was quantitatively complexed by CuCl(2) and the material has shown after thermal activation that a reversible binding of O(2) on the metal ions occurred. This chemisorption process was monitored by UV/Vis and EPR spectroscopies, and the Cu:O(2) adduct was postulated to be an end-on mu-eta(1):eta(1)-peroxodicopper(II) complex bridged by a chloride ion. The Cu(I)-active species, formed during the activation step, were fully recovered during several O(2) binding cycles. The high reactivity of the copper complexes and the room-temperature stability of the dioxygen adduct were explained by the fine adaptability of the tripodal ligand to different geometries, the confinement of the active sites in the hybrid silica that protect them from degradation by a control of the metal-ion microenvironment, as well as the short-range lamellar order of the copper complexes in the framework.

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“…The structures of these compounds are influenced by various factors such as the ligands and solvents used, reaction temperature, metal-ligand ratio, thus producing a variety of coordination geometries. Studies to explore the relationship between the oxidation state of the copper(II) centre and the geometry of the complex as well as the coordinating atoms have been carried out [8][9][10][11][12]. As a result it has become possible to control the oxidation/reduction behaviour using certain ligands.…”

Section: Introductionmentioning

confidence: 99%

Halide Copper(ii) Complexes of Aromatic N-Donor Containing Ligands: Structural, Magnetic and Reactivity Studies

2015

JSC

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The preparation of four new copper(II) complexes with different N-donor ligands [CuBr 2 (2benzylpyridine) 2 ] (1), [CuBr 2 (2-benzylpyridine)(2,2c-bipyridine)]H 2 O (2), [CuBr 2 (3-methyl-2-phenylpiridine) 2 ] (3), [Cu(picolinate) 2 ] KI (4) from copper(I) halides as starting material is described. During the preparation of compound 4 a ligand oxidation reaction took place to give the picolinate ligand starting from 2-(2-methylaminoethyl)pyridine. The complexes were characterized by elemental analyses, IR spectroscopy and crystallographic studies. Single crystal X-ray diffraction analysis of the complexes reveals their monomeric penta-and tetracoordinated nature. For all compounds, the copper(II) present a common square planar coordination except for compound 2 which is five coordinated in a quasi-square pyramidal configuration with W of 0.29. The Cu-N distances for these compounds are in the range of 1.959(4)-2.041(3) Å, Cu-O distance was 1.961(3) Å and Cu-Br distances were in the range of 2.4052(4)-2.4381(6) Å for the square base configuration while for apical distance it was 2.6745(7) Å. Magnetic properties have been investigated for all compounds in the temperature range 2-300 K. Compound 1 shows weak antiferromagnetic intermolecular interaction.

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Synthesis, Structure, and Greatly Improved Reversible O₂ Binding in a Structurally Modulated μ‐η²:η²‐Peroxodicopper(II) Complex with Room‐Temperature Stability

Cited by 67 publications

References 23 publications

Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide

Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide

Reversible Coordination of Dioxygen by Tripodal Tetraamine Copper Complexes Incorporated in a Porous Silica Framework

Halide Copper(ii) Complexes of Aromatic N-Donor Containing Ligands: Structural, Magnetic and Reactivity Studies

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Synthesis, Structure, and Greatly Improved Reversible O2 Binding in a Structurally Modulated μ‐η2:η2‐Peroxodicopper(II) Complex with Room‐Temperature Stability

Cited by 67 publications

References 23 publications

Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide

Specific Enhancement of Catalytic Activity by a Dicopper Core: Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide

Reversible Coordination of Dioxygen by Tripodal Tetraamine Copper Complexes Incorporated in a Porous Silica Framework

Halide Copper(ii) Complexes of Aromatic N-Donor Containing Ligands: Structural, Magnetic and Reactivity Studies

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Synthesis, Structure, and Greatly Improved Reversible O₂ Binding in a Structurally Modulated μ‐η²:η²‐Peroxodicopper(II) Complex with Room‐Temperature Stability