title: Rapid C-H bond activation by a monocopper(III)-hydroxide complex.
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.
authors: Department of Chemistry, Center for Metals in Biocatalysis, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
authors: Patrick J
authors: PJ
authors: Donoghue
authors: Jacqui
authors: J
authors: Tehranchi
authors: Christopher J
authors: CJ
authors: Cramer
authors: Ritimukta
authors: R
authors: Sarangi
authors: Edward I
authors: EI
authors: Solomon
authors: William B
authors: WB
authors: Tolman
mesh_terms: D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006878:Hydroxides / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D006878:Hydroxides; D009942:Organometallic Compounds; D003300:Copper; C031356:hydroxide ion