Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 133, Issue 44, Pages 17602-17605Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja207882h
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Funding
- NIH [R37-GM47365, DK-31450]
- NSF [CHE-0952054]
- Department of Energy, Office of Basic Energy Sciences
- National Institutes of Health, National Center for Research Resources
- Department of Energy, Office of Biological and Environmental Research
- National Center for Research Resources (NCRR), a component of the National Institutes of Health (NIH) [P41 RR001209]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0952054] Funding Source: National Science Foundation
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One-electron oxidation of the tetragonal Cu(II) complex [Bu4N][LCuOH] at -80 degrees C generated the reactive intermediate LCuOH, which was shown to be a Cu(III) complex on the basis of spectroscopy and theory (L = N,N'-bis(2;6-diisopropylphenyl)-2,6-pyridinedicarboxamide). The complex LCuOH reacts with dihydroanthracene to yield, anthracene and the Cu(II) complex LCu-(OH2). Kinetic studies showed that the reaction occurs via H-atom abstraction via a second order rate law at high rates (cf. k = 1.1(1) M-1 s(-1) at -80 degrees C, Delta H-double dagger = 5.4(2). kcal mol(-1), Delta S-double dagger = -30(2) eu) and with very large kinetic isotope effects.(cf. k(H)/k(D) = 44 at -770 degrees C). The findings suggest that a Cu(III)-OH moiety is a viable reactant in oxidation catalysis.
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