Rapid C-H bond activation by a monocopper(III)-hydroxide complex

Patrick J. Donoghue, Jacqui Tehranchi, Christopher J. Cramer, Ritimukta Sarangi, Edward I. Solomon, William B. Tolman

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128 Scopus citations

Abstract

One-electron oxidation of the tetragonal Cu(II) complex [Bu 4N][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.

Original languageEnglish (US)
Pages (from-to)17602-17605
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number44
DOIs
StatePublished - Nov 9 2011

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