title: On the Way to a Trisanionic {Cu3O2} Core for Oxidase Catalysis: Evidence of an Asymmetric Trinuclear Precursor Stabilized by Perfluoropinacolate Ligands.
abstract: CuIcomplexes of the form K[(R3P)Cu(pinF)], in which (pinF)2-is the bidentate, oxygen-donating ligand perfluoropinacolate, were synthesized and characterized. Low-temperature oxygenation of the K[(R3P)Cu(pinF)(PR3)] species resulted in a trisanionic bis(μ3-oxo) trinuclear copper(II,II,III) core characterized by UV/Vis spectroscopy (λmax[nm] = 330, 535, 630), cryospray-ionization mass spectrometry, and X-band electron paramagnetic resonance spectroscopy (derivative resonance at 3300 G, Δms=2 at 1500 G). The kinetic behavior of the trimeric {Cu3O2} species was quantified by stopped-flow spectroscopy and the associated electronic structures were investigated by DFT calculations. An asymmetric {Cu3O2} species,AsTpinF, which bears a structure similar to multicopper oxidases, forms prior to full formation of the symmetric trinuclear core,SyTpinF. The trimer catalytically oxidizes para-hydroquinone to benzoquinone (a form of oxidase chemistry).
authors.affiliation: Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, MA, 02215, USA.
authors.forename: Steven F
authors.initials: SF
authors.lastname: Hannigan
authors.affiliation: Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, MA, 02215, USA.
authors.forename: Amanda I
authors.initials: AI
authors.lastname: Arnoff
authors.affiliation: Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, MA, 02215, USA.
authors.forename: Sarah E
authors.initials: SE
authors.lastname: Neville
authors.affiliation: Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, MA, 02215, USA.
authors.forename: June S
authors.initials: JS
authors.lastname: Lum
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA, 92093, USA.
authors.forename: James A
authors.initials: JA
authors.lastname: Golen
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA, 92093, USA.
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
authors.affiliation: Lehrstuhl für Bioanorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, 91058, Erlangen, Germany.
authors.forename: Nicole
authors.initials: N
authors.lastname: Orth
authors.affiliation: Lehrstuhl für Bioanorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, 91058, Erlangen, Germany.
authors.forename: Ivana
authors.initials: I
authors.lastname: Ivanović-Burmazović
authors.affiliation: Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
authors.forename: Patricia
authors.initials: P
authors.lastname: Liebhäuser
authors.affiliation: Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Rösener
authors.affiliation: Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
authors.forename: Julia
authors.initials: J
authors.lastname: Stanek
authors.affiliation: Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Hoffmann
authors.affiliation: Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
authors.forename: Sonja
authors.initials: S
authors.lastname: Herres-Pawlis
authors.affiliation: Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, MA, 02215, USA.
authors.forename: Linda H
authors.identifier: http://orcid.org/0000-0002-2437-6374
authors.initials: LH
authors.lastname: Doerrer
mesh_terms: D002210:Caprylates / Q000737:chemistry* / Q000378:metabolism; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D004355:Drug Stability; D005466:Fluorocarbons / Q000737:chemistry* / Q000378:metabolism; D006018:Glycols / Q000737:chemistry*; D008024:Ligands; D010088:Oxidoreductases / Q000737:chemistry / Q000378:metabolism*; D010100:Oxygen / Q000737:chemistry*
chemical_list: D002210:Caprylates; D005466:Fluorocarbons; D006018:Glycols; D008024:Ligands; C000621940:pinacol; D003300:Copper; C023036:perfluorooctanoic acid; D010088:Oxidoreductases; D010100:Oxygen
keywords: copper; dioxygen; kinetics; reaction mechanisms; stopped-flow spectroscopy