A Ferromagnetic [Cu3(OH)2]4+ Cluster Formed inside a Tritopic Nonaazapyridinophane: Crystal Structure and Solution Studies

González-Álvarez, Almudena; Alfonso, Ignacio; Cano, Juan; Díaz, Pablo Uriel; Gotor, Vicente; Gotor‐Fernández, Vicente; Garcı́a-España, Enrique; Garcı́a-Granda, Santiago; Jiménez, Hermás R.; Lloret, Francesc

doi:10.1002/ange.200901888

Cited by 12 publications

(2 citation statements)

References 33 publications

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“…The trigonal bipyramidal core was made up of the three coppers at the base and the two μ 3 -hydroxo groups at the apex positions. 236 9.2.3. Other Tricopper Systems.…”

Section: Strategic Considerationsmentioning

confidence: 99%

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics

et al. 2017

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Methane monooxygenases (MMOs) mediate the facile conversion of methane into methanol in methanotrophic bacteria with high efficiency under ambient conditions. Because the selective oxidation of methane is extremely challenging, there is considerable interest in understanding how these enzymes carry out this difficult chemistry. The impetus of these efforts is to learn from the microbes to develop a biomimetic catalyst to accomplish the same chemical transformation. Here, we review the progress made over the past two to three decades toward delineating the structures and functions of the catalytic sites in two MMOs: soluble methane monooxygenase (sMMO) and particulate methane monooxygenase (pMMO). sMMO is a water-soluble three-component protein complex consisting of a hydroxylase with a nonheme diiron catalytic site; pMMO is a membrane-bound metalloenzyme with a unique tricopper cluster as the site of hydroxylation. The metal cluster in each of these MMOs harnesses O to functionalize the C-H bond using different chemistry. We highlight some of the common basic principles that they share. Finally, the development of functional models of the catalytic sites of MMOs is described. These efforts have culminated in the first successful biomimetic catalyst capable of efficient methane oxidation without overoxidation at room temperature.

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“…The trigonal bipyramidal core was made up of the three coppers at the base and the two μ 3 -hydroxo groups at the apex positions. 236 9.2.3. Other Tricopper Systems.…”

Section: Strategic Considerationsmentioning

confidence: 99%

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics

et al. 2017

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“…The 1 H NMR spectra of both 2⋅3 OTf and 2⋅PO 4 contain thirteen signals (see Supporting Information), indicating that the molecules are C 3 ‐symmetric in solution; a higher‐symmetry structure would give rise to nine peaks. The peaks are very well resolved, indicating the presence of low‐lying excited states of the copper(II) complex that allow for fast electronic relaxation 6b. 11 The signals were assigned by comparing longitudinal relaxation times to distances in the X‐ray diffraction structure, as well as using gCOSY experiments and NMR spectra of complexes with a deuterium‐labeled ligand (Supporting Information).…”

Section: Methodsmentioning

confidence: 99%

Trinucleating Copper: Synthesis and Magnetostructural Characterization of Complexes Supported by a Hexapyridyl 1,3,5‐Triarylbenzene Ligand

2011

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Drei Kupferzentren koordiniert ein Hexapyridylligand mit 1,3,5‐Triphenylbenzol‐Gerüst. Der Trikupfer(I)‐Komplex (siehe Bild) reduziert Disauerstoff unter Bildung eines Trikupfer(II)‐Clusters. Die zusätzlichen anionischen Liganden beeinflussen die magnetischen Eigenschaften und EPR‐Spektren dieser Spezies, für die eine lineare Abhängigkeit zwischen den antiferromagnetischen Austauschparametern und den Cu‐O‐Cu‐Winkeln gefunden wird.

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Aerobic Oxidation of Primary Alcohols Catalyzed by Copper Salts and Catalytically Active μ‐Hydroxyl‐Bridged Trinuclear Copper Intermediate

et al. 2010

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Abstract:We have developed a new protocol involving the "copper(II) chloride-cesium carbonate" system for the aerobic oxidation of primary alcohols. Cesium carbonates and the solvents such as toluene and 1,2-dichloroethane play important roles to form a catalytically active intermediate containing a m-hydroxyl-bridged trinuclear copper moiety (complex 1). From the X-ray crystal structure of complex 1, an electrostatic interaction between chloride anions and cesium cations was observed, which stimulated us to understand the roles of cesium carbonate in this reaction as a base, stabilizing and "solvating" intermediates in toluene and 1,2-dichloroethane.

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A Ferromagnetic [Cu₃(OH)₂]⁴⁺ Cluster Formed inside a Tritopic Nonaazapyridinophane: Crystal Structure and Solution Studies

Cited by 12 publications

References 33 publications

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics

Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics

Trinucleating Copper: Synthesis and Magnetostructural Characterization of Complexes Supported by a Hexapyridyl 1,3,5‐Triarylbenzene Ligand

Aerobic Oxidation of Primary Alcohols Catalyzed by Copper Salts and Catalytically Active μ‐Hydroxyl‐Bridged Trinuclear Copper Intermediate

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