Rapid C-H bond activation by a monocopper(III)-hydroxide complex |
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Authors: | Donoghue Patrick J Tehranchi Jacqui Cramer Christopher J Sarangi Ritimukta Solomon Edward I Tolman William B |
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Institution: | Department of Chemistry, Center for Metals in Biocatalysis, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States. |
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Abstract: | One-electron oxidation of the tetragonal Cu(II) complex Bu(4)N]LCuOH] at -80 °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(OH(2)). 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 °C, ΔH(?) = 5.4(2) kcal mol(-1), ΔS(?) = -30(2) eu) and with very large kinetic isotope effects (cf. k(H)/k(D) = 44 at -70 °C). The findings suggest that a Cu(III)-OH moiety is a viable reactant in oxidation catalysis. |
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