TY - JOUR
T1 - Rapid C-H bond activation by a monocopper(III)-hydroxide complex
AU - Donoghue, Patrick J.
AU - Tehranchi, Jacqui
AU - Cramer, Christopher J.
AU - Sarangi, Ritimukta
AU - Solomon, Edward I.
AU - Tolman, William B.
PY - 2011/11/9
Y1 - 2011/11/9
N2 - 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.
AB - 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.
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U2 - 10.1021/ja207882h
DO - 10.1021/ja207882h
M3 - Article
C2 - 22004091
AN - SCOPUS:80455168001
SN - 0002-7863
VL - 133
SP - 17602
EP - 17605
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 44
ER -