The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene

The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene gives 6-amino-1,3-dibutyl-5-cyano-2-ethoxy-4-(1-imino-2-cyanoethyl)-2-oxo-1,3,2-diazaphosphindane.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 303–305, February, 1994.     

Electrooxidation of 2,3-dihydro-1H-1,3,2-diazaphospholes

Electrooxidation of 2-R-1,3-dibutyl-4,5-dimethyl-2,3-dihydro-1H-1,3,2-diazaphospholes with tri- and tetracoordinated phosphorus atoms were studied. Reversible one-electron oxidation gives radical cations at potentials of −0.37 to +0.36 V. Magnetic parameters of the radical cations were measured. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1522–1524, August, 1998.     

Hydrogenation of ethylene on gadolinium X, Y and L-type zeolites

It is shown that Gd-zeolites have a catalytic activity towards ethylene hydrogenation at 1 atm. This activity decreases with an increase in the SiO₂/Al₂O₃ ratio from 2.2 to 6.1 and 4.1, i.e. upon going from an X type zeolite to Y and L. For these types of zeolite the activity grows with an increase in Gd³⁺ content from 50 to 80%. Oxygen addition to the reaction mixture stabilizes the catalytic activity of zeolites.

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, qv 1 . , SiO₂/Al₂O₃ 2,2 6,1 4,1, .. X Y L. , 50 80%. .

     

Electrochemical approaches to generation of phosphinidene complexes of tungsten pentacarbonyl

An alternative approach to synthesis of electrophilic terminal phosphinidene complexes of tungsten pentacarbonyl with various substituents at the phosphorus atom has been developed. The approach is based on the reaction of the electrochemically generated tungsten pentacarbonyl ion with trivalent phosphorus acyl chlorides. Electrochemical reduction of ethyldichlorophosphines in the presence of α-diimines is a one-step process that forms 1,3,2-diazaphospholenes containing an exocyclic P-C bond.     

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.     

Photoinduced electron transfer involving radical ions in multicomponent solutions

A phenomenological study of a specific radical ion mechanism of formation of metastable products is presented. Energy level diagrams of fullerene C₆₀, tetramethylbenzidine, perylene, and radical ion pairs in toluene and benzonitrile are constructed. The possibility for obtaining fast optical switching and limiting in solutions of C₆₀ fullerene, tetramethylbenzidine, and perylene in toluene is analyzed.     

Hydrodynamic formation of stable anisotropic structures in Couette flow of dilute suspensionFormation hydrodynamique pour structures anisotropiques stables dans un flux de Couette d'une suspension diluée

The problem of rotary motion of rigid axially symmetric elongated particles in the Couette flow of dilute suspension with anisotropic carrier fluid is solved. It is shown that the stable stationary solutions of the dynamical set of ordinary differential equations describing the particles rotary motion are possible in the case of forming the stationary anisotropy in the carrier fluid of the suspension. It allows us to detect the stationary orientation of suspended particles and formation of stable anisotropic liquid-crystalline structures in the considered suspension under the action of hydrodynamic forces. The study of rheological properties of such a structured suspension shows that it behaves as a viscoelastic quasi-Newtonian anisotropic liquid medium. To cite this article: E.Yu. Taran et al., C. R. Mecanique 332 (2004).     

The use of a photoinduced electron-transfer reaction for optical limiting in fullerene-containing solutions

Optical limiting was experimentally studied in C₆₀ fullerene-based multicomponent solutions that are characterized by photoinduced electron-transfer processes with the formation of ion-radical pairs. The limitation efficiency in these solutions increased as a result of enhancement of absorption in the molecular system in an excited state. It was found that the spectral and time capabilities of limiters based on fullerene-containing media can be extended with the use of radical ions.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 1, 2005, pp. 32–35.Original Russian Text Copyright © 2005 by Gryaznova, Danilov, Khrebtov, Shakhverdov.     

Ligand-directed electrochemical functionalization of C(sp<Superscript>2</Superscript>)—H bonds in the presence of the palladium and nickel compounds

The recent achievements of electrochemical functionalization of C—H bonds in aromatic substrates containing the pyridine moiety and acting as a ligand directing substitution to the ortho-position in the presence of the palladium and nickel compounds are analyzed and generalized in the review. Acetoxylation, perfluoroacetoxylation, perfluoroalkylation, and phosphorylation are considered for 2-phenylpyridine (PhPy) as an example. The Pd^II metallocycles with the Pd-bound acetate, perfluoroacetate, and perfluoroheptanoate substituents were isolated and characterized as possible intermediates: binuclear [(PhPy)Pd(µ-OAc)]₂ and [(PhPy)Pd(µ-TFA)]₂ and mononuclear [(PhPy)Pd(TFA)](MeCN), [(PhPy)Pd(TFA)](PhPy), [(PhPy)Pd(PFH)](PhPy), and [(PhPy)Pd(EtO)₂P(O)]₂. Their electrochemical properties were studied. The fluorinated derivatives are in solvent-dependent equilibrium between the mononuclear and binuclear forms. Cyclic voltammetry was used to establish the redox properties of the palladium cycles and routes of their oxidation to the final products. A new approach to CH-substitution products based on the electrochemical generation of Pd or Ni in high oxidation states in the presence of substrate-ligand was proposed.