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Issue 2, 2013
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Metal-templated ligand architectures for trinuclear chemistry: tricopper complexes and their O2 reactivity

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Abstract

A trinucleating framework was assembled by templation of a heptadentate ligand around yttrium and lanthanides. The generated complexes orient three sets of two or three N-donors each for binding additional metal centers. Addition of three equivalents of copper(I) leads to the formation of tricopper(I) species. Reactions with dioxygen at low temperatures generate species whose spectroscopic features are consistent with a μ33-dioxo-tricopper complex. Reactivity studies were performed with a variety of substrates. The dioxo-tricopper species deprotonates weak acids, undergoes oxygen atom transfer with triphenylphosphine to yield triphenylphosphine oxide, and performs hydrogen atom abstraction from tetramethylpiperidine-N-hydroxide (TEMPO-H). Thiophenols reduce the oxygenated species to a Cu3I complex and liberate two equivalents of disulfide, consistent with a four-electron four-proton process.

Graphical abstract: Metal-templated ligand architectures for trinuclear chemistry: tricopper complexes and their O2 reactivity

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Publication details

The article was received on 16 Oct 2012, accepted on 25 Nov 2012 and first published on 26 Nov 2012


Article type: Edge Article
DOI: 10.1039/C2SC21758A
Citation: Chem. Sci., 2013,4, 785-790
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    Metal-templated ligand architectures for trinuclear chemistry: tricopper complexes and their O2 reactivity

    D. Lionetti, M. W. Day and T. Agapie, Chem. Sci., 2013, 4, 785
    DOI: 10.1039/C2SC21758A

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