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Metal-templated ligand architectures for trinuclear chemistry: tricopper complexes and their O_2 reactivity

Lionetti, Davide and Day, Michael W. and Agapie, Theodor (2013) Metal-templated ligand architectures for trinuclear chemistry: tricopper complexes and their O_2 reactivity. Chemical Science, 4 (2). pp. 785-790. ISSN 2041-6520 . PMCID PMC3607385.

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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 μ_3,μ_3-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 Cu_3^I complex and liberate two equivalents of disulfide, consistent with a four-electron four-proton process.

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URLURL TypeDescription CentralArticle
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2013 Royal Society of Chemistry. Received 16 Oct 2012, Accepted 25 November 2012; first published on the web 26 November 2012. We thank Lawrence M. Henling for crystallographic assistance. We are grateful to Caltech and the ACS Petroleum Research Fund for funding. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to Caltech, CHE- 0639094. The 400 MHz NMR spectrometer was purchased via an NIH award, RR027690.
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American Chemical Society Petroleum Research FundUNSPECIFIED
Issue or Number:2
PubMed Central ID:PMC3607385
Record Number:CaltechAUTHORS:20130206-145708635
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:36800
Deposited By: Jason Perez
Deposited On:07 Feb 2013 23:41
Last Modified:03 Oct 2019 04:41

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