Electrochemical phosphorylation of coumarins catalyzed by transition metal complexes (Ni—Mn,Co—Mn)

Russian Chemical Bulletin - A possibility of electrochemical phosphorylation of coumarins (coumarin, 6-methylcoumarin, 7-methylcoumarin) with diethyl phosphite was shown. The approach is based on...     

Selective fluorination of pyridine and its derivatives in the presence of high-oxidation-state transition metals

The oxidative fluorination of pyridine and 4-ethylpyridine under chemical and electro-chemical conditions in the presence of transition metal (high-oxidation-state nickel, cobalt, and silver) salts was studied. The chemical fluorination affords 2-fluoropyridine in all cases, while the electrochemical fluorination results in 2-fluoroor 3-fluoropyridine depending on the catalyst used.     

Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine

The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)Fe^III₂] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2–300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH₂Cl₂ solution was monitored by EPR spectroscopy.     

A Water-Soluble Sodium Pectate Complex with Copper as an Electrochemical Catalyst for Carbon Dioxide Reduction

A selective noble-metal-free molecular catalyst has emerged as a fruitful approach in the quest for designing efficient and stable catalytic materials for CO₂ reduction. In this work, we report that a sodium pectate complex of copper (PG-NaCu) proved to be highly active in the electrocatalytic conversion of CO₂ to CH₄ in water. Stability and selectivity of conversion of CO₂ to CH₄ as a product at a glassy carbon electrode were discovered. The copper complex PG-NaCu was synthesized and characterized by physicochemical methods. The electrochemical CO₂ reduction reaction (CO₂RR) proceeds at −1.5 V vs. Ag/AgCl at ~10 mA/cm² current densities in the presence of the catalyst. The current density decreases by less than 20% within 12 h of electrolysis (the main decrease occurs in the first 3 h of electrolysis in the presence of CO₂). This copper pectate complex (PG-NaCu) combines the advantages of heterogeneous and homogeneous catalysts, the stability of heterogeneous solid materials and the performance (high activity and selectivity) of molecular catalysts.     

Electrochemical oxidative phosphorylation of azoles in the presence of silver catalysts

A new method for the phosphorylation of benzo-1,3-azoles (benzoxazole, benzothiazole, and 3-methylindole) with diethyl phosphite by electrocatalytic oxidation was proposed. The process occurs under electrochemical mild conditions (room temperature, normal pressure) in the presence of silver salts or silver oxide. This method allows one to obtain 2-phosphorylated products of benzo-1,3-azoles in good yield (up to 75%).     

Electrocatalytic fluoroalkylation of olefins. Perfluoroalkylation of 2-vinylpyridine

Perfluoroalkylation of 2-vinylpyridine was conducted under conditions for the formation of low-valent nickel complexes during electroreduction of NiBr₂L (L is the bipy, terpy) in DMF solutions. Depending on the electrosynthesis conditions, either dimeric products of addition of perfluoroalkyl substituents at the double bond of the olefin or (in the presence of triethylamine) 1-perfluorohexyl-2-pyridinethylene were formed.