Activation of dioxygen by copper metalloproteins and insights from model complexes

Reaction Mechanisms of Metalloenzymes and Synthetic Model Complexes Activating Dioxygen Reaction Mechanisms of Metalloenzymes and Synthetic Model Complexes Activating Dioxygen

Copper(II) hexaaza macrocyclic binuclear complexes obtained from the reaction of their copper(I) derivates and molecular dioxygen.

Density functional theory (DFT) calculations have been carried out for a series of Cu(I) complexes bearing N-hexadentate macrocyclic dinucleating ligands and for their corresponding peroxo species (1c-8c) generated by their interaction with molecular O2. For complexes 1c-7c, it has been found that the side-on peroxodicopper(II) is the favored structure with regard to the bis(mu-oxo)dicopper(III...

Dioxygen reduction catalyzed by dicobalt Pacman complexes

The development of fuel cell technologies for automotive use in particular is integral to clean and sustainable energy generation, and relies on catalysts to carry out fundamental chemical redox reactions at the electrodes. At present, the four-electron reduction of dioxygen to water that occurs at the cathode is the most problematic as it is catalysed by expensive Pt metal that requires consid...

Catalytic oxidation of alkanes by iron bispidine complexes and dioxygen: oxygen activation versus autoxidation.

Organic substrates (specifically cis-1,2-dimethylcyclohexane, DMCH) are oxidized by O2 in the presence of iron(II)-bispidine complexes. It is shown that this oxidation reaction is not based on O2 activation by the nonheme iron catalysts as in Nature but due to a radical-based initiation, followed by a radical- and ferryl-based catalytic reaction.

Activation of Dioxygen by Halocarbon Ions

Tandem mass spectrometry is used to show that low energy collisions of ionized halocarbenes, including CBr2 and CBrCl•+, with molecular oxygen lead to (i) decarbonation with formation of the dihalogen molecular cation and (ii) oxygenolysis yielding BrCO+. Both reactions may occur via the same ion-molecule addition product of molecular oxygen and the ionized carbene. Reaction is favored at low c...