An [FeII3O]4+ Core Wrapped by Two [FeIIL3]− Units

Yoneda, K.; Adachi, Keita; Nishio, Kyonosuke; Yamasaki, Mikio; Fuyuhiro, Akira; Katada, Motomi; Kaizaki, Sumio; Kawata, Satoshi

doi:10.1002/anie.200602067

Cited by 68 publications

(41 citation statements)

References 42 publications

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“…Despite the increasing number of studies on cluster helicates that have appeared in the literature, practical applications for these compounds have not been reported to date. [11] Here we report the synthesis, characterization and reactivity studies of novel polynuclear copper(I) cluster helicates derived from a thiosemicarbazone ligand that are capable of promoting, in the presence of O 2 , the arene hydroxylation of their supporting ligand strands. The cluster helicates reported here represent new models of tyrosinase, an enzyme that catalyzes the hydroxylation of aromatic compounds.…”

Section: Introductionmentioning

confidence: 99%

Endogenous Arene Hydroxylation Promoted by Copper(I) Cluster Helicates

Martínez‐Calvo¹,

López²,

Pedrido³

et al. 2010

Chemistry A European J

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A novel neutral triple-stranded hexanuclear copper(I) cluster helicate [Cu(I)(6)L(3)]·2CH(3)CN derived from a thiosemicarbazone ligand could be synthesized and crystallographically characterized. The MALDI mass spectrum of this complex suggests that the tetranuclear copper(I) cluster helicate [Cu(I)(4)L(2)] is also present in solution. These copper(I) cluster helicates are capable, in the presence of O(2), of hydroxylating the arene linker of their supporting ligand strands. The resulting dinuclear complex [Cu(II)(2)L'(OH)] is formed by two copper(II) centers, a new ligand arising from the hydroxylation reaction, and one hydroxide group. The magnetic investigation of this compound shows a strong antiferromagnetic coupling between the two Cu(II) centers. The kinetic studies for the hydroxylation process show values of ΔH(≠)=-70 kJ mol(-1), similar to those mediated by the tyrosinase enzymes.

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Section: Introductionmentioning

confidence: 99%

Endogenous Arene Hydroxylation Promoted by Copper(I) Cluster Helicates

Martínez‐Calvo¹,

López²,

Pedrido³

et al. 2010

Chemistry A European J

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“…16 They used a 3,5-di(2-pyridyl)pyrazolate ligand (1 ¹ ), 18 which has two chemically equivalent bidentate coordination sites. Figure 3), while the other side joints the two subunits together in the middle (depicted in blue in Figure 3).…”

Section: ç Desymmetrization By Stabilization Of Local Structural Motifsmentioning

confidence: 99%

“…These factors made it possible to stabilize the whole M 5 L 6 bis(triple- . 16 (a) A schematic representation and chemical structures. 17 (b) Xray crystal structure.…”

Section: ç Desymmetrization By Stabilization Of Local Structural Motifsmentioning

confidence: 99%

Elaborate Metallosupramolecular Architectures through Desymmetrization Self-assembly of Symmetric Building Blocks

2013

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Desymmetrization self-assembly of symmetric building blocks is a powerful method to construct elaborate metallosupramolecular architectures. Herein several examples are given to discuss how to build up self-assembled complexes with low symmetry, focusing on 1) stabilization of local structural motifs by template molecules and/or interligand interactions, 2) rigidity regulation of ligand scaffolds, and 3) control of intermediate complexation conditions. Unsymmetrically assembled supramolecular host complexes exhibit unique functions reflecting their structural frameworks. Ç IntroductionThree-dimensional arrangement of molecular components is an efficient tool to construct platforms for elaborate chemical functions within isolated inner spaces. For example, natural enzymes perform highly selective molecular recognition and catalytic reactions utilizing cooperative effects of functional amino acid residues arranged around their active sites (Figure 1a), 1 where the positions of the functional groups and environments of active sites are well-defined by the folded protein scaffold. However, when considering the structural modification for further applications, it is still difficult to design and predict the folding behaviors of chemically modified macromolecules.2 Self-assembly of artificial molecular components is a powerful method for the construction of discrete and welldefined three-dimensional architectures.3 In this supramolecular approach, purposely designed building blocks are equipped with multiple functional groups to exert reversible intermolecular interactions between them. Coordination bonds, 4 hydrogen bonds, 5 electrostatic interactions, 6 and hydrophobic effects 7 are utilized to assemble individual building blocks into finite desired structures under appropriate conditions. In particular, coordination-driven self-assembly of organic ligands and metal ions has advantages in terms of the directionality and stability of coordination bonds, and design versatility of organic ligands.Organic ligands with multiple metal binding sites are required for assembling each component via coordination bonding. In general, when ligands that have chemically equivalent metal binding sites and therefore high symmetry are employed, the resulting supramolecular complexes also tend to possess uniform, highly symmetric frameworks. This is because; 1) direction and strength of coordination bonds between chemically equivalent binding sites and metal ions are usually equal; and 2) the self-assembly process is thermodynamically controlled where the products are formed as the result of repetitive bond formation and dissociation.In this context, construction of unsymmetrically selfassembled architectures is a challenging issue. Realization of such structures has a substantial impact, because it allows selfassembled unities to have elaborate functions by arranging molecular components in less symmetric but well-organized manners, which is reminiscent of natural enzymes.8 Common strategies to construct more intricate self-a...

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“…For metal complexes of 3,5-bis(2-pyridyl)pyrazole, see: Klingele et al (2009) ;Yoneda, Adachi, Hayami et al (2006); Yoneda, Adachi, Nishio et al (2006); Ishikawa et al (2010); Mishima et al (2011);Washizaki et al (2012). For an example of a coordinated hexafluorophosphate ion, see: Noro et al (2011).…”

Section: Related Literaturementioning

confidence: 99%

“…The Hbpypz has four N donors by deprotonation; the two N atoms in a pyrazole moiety and two N atoms in pyridine moieties. This ligand can bind to metal ions by behaving as a bidentate or as a tetradentate ligand and would be possible to form various coordination modes (Yoneda, Adachi, Hayami et al, 2006;Yoneda, Adachi, Nishio et al, 2006). In particular, two bpypzions form a planar dinuclear complex by chelating two metal ions at equatorial position (Washizaki et al, 2012).…”

Section: S1 Commentmentioning

confidence: 99%

Bis[μ-3,5-bis(pyridin-2-yl)pyrazolato]bis[(hexafluorophosphato)copper(II)]

et al. 2013

Self Cite

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Key indicators: single-crystal X-ray study; T = 200 K; mean (C-C) = 0.003 Å; R factor = 0.027; wR factor = 0.074; data-to-parameter ratio = 14.9.The title dinuclear complex molecule, [Cu 2 (C 13 H 9 N 4 ) 2 (PF 6 ) 2 ], lies about an inversion center. The Cu II atom shows a squarepyramidal coordination geometry with the basal plane formed by four N atoms of the two bis-chelating 3,5-bis(pyridin-2-yl)pyrazolate ions and with one F atom of the hexafluorophosphate ion in the apical position. Molecules are stacked in a column along the a axis through C-HÁ Á ÁF hydrogen bonds. The columns are further linked by other C-HÁ Á ÁF hydrogen bonds, forming a three-dimensional network. Related literature

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An [Fe^II₃O]⁴⁺ Core Wrapped by Two [Fe^IIL₃]⁻ Units

Cited by 68 publications

References 42 publications

Endogenous Arene Hydroxylation Promoted by Copper(I) Cluster Helicates

Endogenous Arene Hydroxylation Promoted by Copper(I) Cluster Helicates

Elaborate Metallosupramolecular Architectures through Desymmetrization Self-assembly of Symmetric Building Blocks

Bis[μ-3,5-bis(pyridin-2-yl)pyrazolato]bis[(hexafluorophosphato)copper(II)]

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