1339804-25-9Relevant academic research and scientific papers
Rapid C-H bond activation by a monocopper(III)-hydroxide complex
Donoghue, Patrick J.,Tehranchi, Jacqui,Cramer, Christopher J.,Sarangi, Ritimukta,Solomon, Edward I.,Tolman, William B.
, p. 17602 - 17605 (2011/12/15)
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(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 °C, ΔH? = 5.4(2) kcal mol-1, ΔS? = -30(2) eu) and with very large kinetic isotope effects (cf. kH/kD = 44 at -70 °C). The findings suggest that a Cu(III)-OH moiety is a viable reactant in oxidation catalysis.
