Metal-templated ligand architectures for trinuclear chemistry: tricopper complexes and their O_2 reactivity
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 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.
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.Attached Files
Supplemental Material - c2sc21758a.pdf
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Additional details
- PMCID
- PMC3607385
- Eprint ID
- 36800
- Resolver ID
- CaltechAUTHORS:20130206-145708635
- American Chemical Society Petroleum Research Fund
- CHE-0639094
- NSF
- RR027690
- NIH
- Created
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2013-02-07Created from EPrint's datestamp field
- Updated
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2021-11-09Created from EPrint's last_modified field