Flavonol dioxygenase chemistry mediated by a synthetic nickel superoxide.

Nature exploits transition metal centers to enhance and tune the oxidizing power of natural oxidants such as O and HO. The design and interrogation of synthetic metallocomplexes with similar reactivity to metalloproteins provides one strategy for gaining insight into the mechanistic underpinnings of oxygen-activating enzymes such as oxidases, oxygenases, and dioxygenases like Ni-quercetinase (Ni-QueD). Ni-QueD catalyzes the oxidative ring opening of the polyphenol quercetin, a natural product with antioxidant properties.

Molecular Catalyst Synthesis Strategies to Prepare Atomically Dispersed Fe-N-C Heterogeneous Catalysts.

We report a strategy to integrate atomically dispersed iron within a heterogeneous nitrogen-doped carbon (N-C) support, inspired by routes for metalation of molecular macrocyclic iron complexes. The N-C support, derived from pyrolysis of a ZIF-8 metal-organic framework, is metalated via solution-phase reaction with FeCl and tributyl amine, as a Brønsted base, at 150 °C. Fe active sites are characterized by Fe Mössbauer spectroscopy and aberration-corrected scanning transmission electron microscopy.

Heterogeneous M-N-C Catalysts for Aerobic Oxidation Reactions: Lessons from Oxygen Reduction Electrocatalysts.

Nonprecious metal heterogeneous catalysts composed of first-row transition metals incorporated into nitrogen-doped carbon matrices (M-N-Cs) have been studied for decades as leading alternatives to Pt for the electrocatalytic O reduction reaction (ORR). More recently, similar M-N-C catalysts have been shown to catalyze the aerobic oxidation of organic molecules. This Focus Review highlights mechanistic similarities and distinctions between these two reaction classes and then surveys the aerobic oxidation reactions catalyzed by M-N-Cs.

Two isomers of [1-benzyl-4-(pyridin-2-yl-κ)-1-1,2,3-triazole-κ ]di-chlorido-bis-(dimethyl sulfoxide-κ)ruthenium(II).

The structures of two isomers of the title compound, [RuCl(CHN)(CHOS)], and , are reported. Isomers and are produced by reaction of the pyridyl-triazole ligand 1-benzyl-4-(pyridin-2-yl)-1-1,2,3-triazole (bpt) () with -[RuCl(DMSO-)(DMSO-)]. Reaction in acetone produces 95% , which is the -6-14 isomer, with DMSO and chlorido ligands, and 5% (the -6-32 isomer, with DMSO and chlorido ligands, and the pyridyl moiety of bpt to DMSO).