Dual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu3O2} moiety with perfluoro-t-butoxide ligands.

A Cu(i) fully fluorinated O-donor monodentate alkoxide complex, K[Cu(OC4F9)2], was previously shown to form a trinuclear copper-dioxygen species with a {Cu3(µ3-O)2} core, TOC4F9, upon reactivity with O2 at low temperature. Herein is reported a significantly expanded kinetic and mechanistic study of TOC4F9 formation using stopped-flow spectroscopy. The TOC4F9 complex performs catalytic oxidase conversion of hydroquinone (H2Q) to benzoquinone (Q). TOC4F9 also demonstrated hydroxylation of 2,4-di-tert-butylphenolate (DBP) to catecholate, making TOC4F9 the first trinuclear species to perform tyrosinase (both monooxygenase and oxidase) chemistry. Resonance Raman spectra were also obtained for TOC4F9, to our knowledge, the first such spectra for any T species. The mechanism and substrate reactivity of TOC4F9 are compared to those of its bidentate counterpart, TpinF, formed from K[Cu(pinF)(PR3)]. The monodentate derivative has both faster initial formation and more diverse substrate reactivity.

Cu(i)-O2 oxidation reactions in a fluorinated all-O-donor ligand environment.

Investigation of Cu-O2 oxidation reactivity is important in biological and anthropogenic chemistry. Zeolites are one of the most promising Cu/O based oxidation catalysts for development of industrial-scale CH4 to CH3OH conversion. Their oxidation mechanisms are not well understood, however, highlighting the importance of the investigation of molecular Cu(i)-O2 reactivity with O-donor complexes. Herein, we give an overview of the synthesis, structural properties, and O2 reactivity of three different series of O-donor fluorinated Cu(i) alkoxides: K[Cu(OR)2], [(Ph3P)Cu(µ-OR)2Cu(PPh3)], and K[(R3P)Cu(pinF)], in which OR = fluorinated monodentate alkoxide ligands and pinF = perfluoropinacolate. This breadth allowed for the exploration of the influence of the denticity of the ligand, coordination number, the presence of phosphine, and KF/O interactions on their O2 reactivity. KF/O interactions were required to activate O2 in the monodentate-ligand-only family, whereas these connections did not affect O2 activation in the bidentate complexes, potentially due to the presence of phosphine. Both families formed trisanionic, trinuclear cores of the form {Cu3(µ3-O)2}3-. Intramolecular and intermolecular substrate oxidation were also explored and found to be influenced by the fluorinated ligand. Namely, {Cu3(µ3-O)2}3- from K[Cu(OR)2] could perform both monooxygenase reactivity and oxidase catalysis, whereas those from K[(R3P)Cu(pinF)] could only perform oxidase catalysis.