Preparation and structures of dinuclear complexes containing MII–OH centers

Ng, Gary K.-Y.; Borovik, A. S.

doi:10.1039/c2cc16277f

Cited by 20 publications

(16 citation statements)

References 37 publications

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“…The two reactive cobalt-bound hydroxo moieties are adjacent to each other, but resist dehydration. 18 A double terminal hydroxo rhombus with a distance of ca. 3 Å is formed, stabilized by the dense intramolecular hydrogen bonds.…”

Section: Aminesmentioning

confidence: 99%

Insights into metalloenzyme microenvironments: biomimetic metal complexes with a functional second coordination sphere

et al. 2013

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Non-covalent interactions in the second coordination sphere of metalloenzymes play a significant role in determining activity and selectivity. The importance of these interactions is reflected in the increasing number of reports on model complexes with a functional second coordination sphere. These hybrid mimics were developed according to the strategies of modification with functional groups, combination with supramolecular hosts and coupling with polymers, to shed light on the role of non-covalent interactions in metalloenzyme catalysis. This review provides an overview of recent progress in this area. An introduction to native metalloenzymes with an emphasis on the second coordination sphere is also given.

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Section: Aminesmentioning

confidence: 99%

Insights into metalloenzyme microenvironments: biomimetic metal complexes with a functional second coordination sphere

et al. 2013

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“…Each metal center has an additional open coordination site that may accommodate terminal ligands in a syn geometry. This structural feature is of interest in the design of synthetic molecular water oxidation catalysts, 29 as well as other catalysts (e.g., for oxidative dehydrogenation). 30,31 The following results describe the dinucleating ability of DPFN for the first-row transition metals from manganese to copper, with chloro, hydroxo, and aqua bridging ligands that give the diamond-shaped core structure.…”

Section: Introductionmentioning

confidence: 99%

Dinuclear first-row transition metal complexes with a naphthyridine-based dinucleating ligand

Davenport

Tilley

2015

Dalton Trans.

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A series of dinuclear and tetranuclear first-row transition metal complexes were synthesized with the dinucleating ligand 2,7-bis(di(2-pyridyl)fluoromethyl)-1,8-naphthyridine (DPFN). The coordination pocket and rigidity of the DPFN ligand enforces pseudo-octahedral geometries about the metal centers that contain chloro, hydroxo, and aqua bridging ligands forming a "diamond" shaped configuration with metal-metal distances varying from 2.7826(5) to 3.2410(11) Å. Each metal center in the dinuclear complexes has an additional open coordination site that accommodates terminal ligands in a syn geometry of particular interest in catalyst design. The complexes are characterized by electronic spectroscopy, electrochemistry and potentiometric titration methods.

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“…Such studies would benefit from the availability of structural and functional models of the active sites for cobalt-based catalysts, which until now has been greatly limited. 12 For heterogeneous catalysts, the active site is thought to involve more than one metal center; therefore, a challenging goal is the synthesis of relevant, well-defined assemblies of cobalt centers. 13,14 In this contribution, we report the synthesis and study of a model for proposed dinuclear active sites, 15 which allows interrogation of structural, chemical, and catalytic properties.…”

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confidence: 99%

A molecular structural analog of proposed dinuclear active sites in cobalt-based water oxidation catalysts

et al. 2014

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The compound [Co2(μ-OH)2(OH2)2(DPFN)][NO3]4 is a molecular structural analog of proposed active sites of cobalt phosphate water oxidation catalysts. Computational studies on this system indicate feasible catalytic pathways to oxygen formation, despite the low electrocatalytic activity observed for [Co2(μ-OH)2(OH2)2(DPFN)][NO3]4. Electrochemical and reactivity studies implicate the binding of phosphate to the dicobalt core, which may inhibit water oxidation catalysis.

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Preparation and structures of dinuclear complexes containing MII–OH centers

Cited by 20 publications

References 37 publications

Insights into metalloenzyme microenvironments: biomimetic metal complexes with a functional second coordination sphere

Insights into metalloenzyme microenvironments: biomimetic metal complexes with a functional second coordination sphere

Dinuclear first-row transition metal complexes with a naphthyridine-based dinucleating ligand

A molecular structural analog of proposed dinuclear active sites in cobalt-based water oxidation catalysts

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