title: Effects of Imidazole-Type Ligands in CuI/TEMPO-Mediated Aerobic Alcohol Oxidation.
abstract: Selective aerobic oxidation of benzyl alcohol to benzaldehyde by a (bpy)CuI(IM)/TEMPO catalyst (IM represents differently substituted imidazoles) has been studied by simultaneous operando electron paramagnetic resonance/UV-vis/attentuated total reflectance infrared spectroscopy in combination with cyclic voltammetry to explore the particular role of imidazole in terms of ligand and/or base as well as of its substitution pattern on the catalytic performance. For molar ratios of IM/Cu ≥ 2, a (bpy)CuI/II(IM)a(IM)bcomplex is formed, in which the Cu-N distances and/or angles for the two IM ligands a and b are different. The coordination of a second IM molecule boosts the oxidation of CuIto CuIIand, thus, helps to activate O2by electron transfer from CuIto O2. The rates of CuIoxidation and CuIIreduction and, thus, the rates of benzaldehyde formation depend on R of the R-N moiety in the IM ligand. Oxidation is fastest for R = H and alkyl, while reduction is slowest for R = H. The CuI/CuIIinterplay leads to decreasing total benzaldehyde formation rates in the order R (I+ effect) > R (conjugated system) > R = H.
authors.affiliation: Leibniz-Institut für Katalyse, Universität Rostock , Albert-Einstein Straße 29A, 18059 Rostock, Germany.
authors.forename: Sven
authors.initials: S
authors.lastname: Adomeit
authors.affiliation: Leibniz-Institut für Katalyse, Universität Rostock , Albert-Einstein Straße 29A, 18059 Rostock, Germany.
authors.forename: Jabor
authors.initials: J
authors.lastname: Rabeah
authors.affiliation: Leibniz-Institut für Katalyse, Universität Rostock , Albert-Einstein Straße 29A, 18059 Rostock, Germany.
authors.forename: Annette E
authors.initials: AE
authors.lastname: Surkus
authors.affiliation: Leibniz-Institut für Katalyse, Universität Rostock , Albert-Einstein Straße 29A, 18059 Rostock, Germany.
authors.forename: Ursula
authors.initials: U
authors.lastname: Bentrup
authors.affiliation: Leibniz-Institut für Katalyse, Universität Rostock , Albert-Einstein Straße 29A, 18059 Rostock, Germany.
authors.forename: Angelika
authors.initials: A
authors.lastname: Brückner