O2 Activation and Selective Phenolate ortho Hydroxylation by an Unsymmetric Dicopper μ-η1:η1-Peroxido Complex
نویسندگان
چکیده
منابع مشابه
Complete σ* intramolecular aromatic hydroxylation mechanism through O2 activation by a Schiff base macrocyclic dicopper(I) complex
In this work we analyze the whole molecular mechanism for intramolecular aromatic hydroxylation through O2 activation by a Schiff hexaazamacrocyclic dicopper(I) complex, [Cu(I) 2(bsH2m)](2+). Assisted by DFT calculations, we unravel the reaction pathway for the overall intramolecular aromatic hydroxylation, i.e., from the initial O2 reaction with the dicopper(I) species to first form a Cu(I)Cu(...
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CuII2(μ-η2:η2-peroxido) and CuIII2(μ-oxido)2 cores represent key intermediates in copper/dioxygen chemistry, and they are mechanistically important for biological hydroxylation and oxidation reactions mediated by dinuclear (type III) copper metalloenzymes. While the exact nature of the active species in different enzymes is still under debate, shifting equilibria between Cu x /O2 species is inc...
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Iron species with terminal oxo ligands are implicated as key intermediates in several synthetic and biochemical catalytic cycles. However, there is a dearth of structural information regarding these types of complexes because their instability has precluded isolation under ambient conditions. The isolation and structural characterization of an iron(III) complex with a terminal oxo ligand, deriv...
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A novel metallohost containing a substrate-binding site and two copper ions held by two bis-pyrazole ligand sets is described. The cavity of this molecule can bind dihydroxybenzene guests (association constants in chloroform are in the range K& = 2000-3000 M-1). In the presence of benzylic alcohols the Cu(II) centers of the metallohost are reduced to Cu(I). During this process the alcohols are ...
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The title compound, [Co(2)(O(2))(CH(3)CN)(2)(C(2)H(8)N(2))(4)](ClO(4))(4), consists of centrosymmetric binuclear cations and perchlorate anions. Two Co(III) atoms, which have a slightly distorted octa-hedral coordination, are connected through a peroxido bridge; the O-O distance is 1.476 (3) Å. Both acetonitrile ligands are situated in a trans position with respect to the O-O bridge. In the cry...
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ژورنال
عنوان ژورنال: Angewandte Chemie International Edition
سال: 2010
ISSN: 1433-7851
DOI: 10.1002/anie.200906749