Dual oxidase/oxygenase reactivity and resonance Raman spectra of {CuO} 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).

Designed To React: Terminal Copper Nitrenes and Their Application in Catalytic C-H Aminations.

Heteroscorpionate ligands of the bis(pyrazolyl)methane family have been applied in the stabilisation of terminal copper tosyl nitrenes. These species are highly active intermediates in the copper-catalysed direct C-H amination and nitrene transfer. Novel perfluoroalkyl-pyrazolyl- and pyridinyl-containing ligands were synthesized to coordinate to a reactive copper nitrene centre.

Copper Guanidinoquinoline Complexes as Entatic State Models of Electron-Transfer Proteins.

The electron-transfer abilities of the copper guanidinoquinoline (GUAqu) complexes [Cu(TMGqu) ] and [Cu(DMEGqu) ] (TMGqu=tetramethylguanidinoquinoline, DMEGqu=dimethylethylguanidinoquinoline) were examined in different solvents. The determination of the electron self-exchange rate based on the Marcus theory reveals the highest electron-transfer rate of copper complexes with pure N-donor ligands (k =1.2×10  s  m in propionitrile).

On the Way to a Trisanionic {Cu O } Core for Oxidase Catalysis: Evidence of an Asymmetric Trinuclear Precursor Stabilized by Perfluoropinacolate Ligands.

Cu complexes of the form K[(R P)Cu(pin )], in which (pin ) is the bidentate, oxygen-donating ligand perfluoropinacolate, were synthesized and characterized. Low-temperature oxygenation of the K[(R P)Cu(pin )(PR )] species resulted in a trisanionic bis(μ -oxo) trinuclear copper(II,II,III) core characterized by UV/Vis spectroscopy (λ [nm] = 330, 535, 630), cryospray-ionization mass spectrometry, and X-band electron paramagnetic resonance spectroscopy (derivative resonance at 3300 G, Δm =2 at 1500 G). The kinetic behavior of the trimeric {Cu O } species was quantified by stopped-flow spectroscopy and the associated electronic structures were investigated by DFT calculations.