V. N. Yakovlev

Regeneration of the Ru(bipy)3Cl2 excitation under chemiluminescence activation in the reaction of diphenylmethane autooxidation in an alkaline medium

The effect of the Ru(bipy)3Cl2 [RuII] complex on chemiluminescence in the autooxidation of diphenylmethane in the presence of BuIOK was studied. The luminescence increases due to the participation of an activator in the redox processes. The excitation of the RII complex occurs in the stage of oxidation by the superoxide anion of the RuI complex formed by the one-electron reduction of the initial RuII by anions.

Chemiluminescence testing of solutions to detect organometallic peroxides during oxidation of organometallic compounds by oxygen

Conclusions1.The possibility of detecting organometallic peroxides without decreasing the temperature and hydrolysis of the reaction solution during oxidation of organometallic compounds with oxygen based on the kinetic maxima of the intensity of chemiluminescence was demonstrated.2.The formation of organometallic peroxides was detected during oxidation of organic derivatives of uranium and lanthanides with oxygen.3.The stage of formation of an organometallic peroxide during oxidation of organometallic compounds with oxygen takes place more rapidly than the reactions of its subsequent consumption.

Effect of oxygen on the chemiluminescence during the oxidation of ethylaluminum diethoxide by xenon difluoride in solution

Conclusions1.The effect of oxygen on the chemiluminescent reaction of alkyl organoaluminum compounds with xenon difluoride was determined. The emission becomes stronger or weaker depending on the concentration of oxygen in the solution.2.In addition to the main source of emission (reactions not containing O2 radicals), there is an additional source due to the transformation of the alkyl radicals (reaction intermediates) into peroxyl radicals, which disproportionate with the emission of light.

Effect of the nature of the organoaluminum compound on the direction of the reaction with xenon difluoride

In the authors previous work, they reported the chemiluminescence of organoaluminum compounds (OAC) upon oxidation by XeF/sub 2/ in solution. In the present work, gas-liquid chromatography, elemental and gas volumetric analysis, F- and Cl-electrode-selective potentiometry, and chemiluminescence were used to determine that the attack by XeF/sub 2/ in the reaction of XeF/sub 2/ with OAC such as Et/sub 3/Al (I), (EtO)/sub 2/AlEt (II), Et/sub 2/AlCl (III), and (t-Bu)/sub 2/AIH (IV) proceeds only at the Al-R bond. The C-H bonds of the alkyl groups of OAC do not participate in this reaction, which indicates the possibility of using the reaction of OAC and XeF/sub 2/ for the synthesis of OAC with an Al-F bond.

Chemiluminescence excitation in the redox reactions of metal carbonyls and their derivatives with xenon difluoride

The authors use gas-liquid chromatography, volumetry, elemental analysis, and UV, visible, and IR absorption spectroscopy to study the oxidation of XeF/sub 2/ by carbonyls of group VI-VIII metals Mo(CO)/sub 6/, (C/sub 6/H/sub 5/CH/sub 3/) Mo(CO)/sub 3/, W(CO)/sub 6/, Mn/sub 2/(CO)/sub 10/, C/sub 5/H/sub 5/Mn(CO)/sub 3/, Fe(CO)/sub 5/, Fe/sub 2/(CO)/sub 9/, and (acac) Rh(CO)/sub 2/. The reactions are accompanied by change in solution color, the release of gaseous Xe and CO, and the formation of fluoro derivatives of metal carbonyls and metal fluorides. Chemiluminescence is excited in the overall process of the consecutive redox replacement of CO groups in the metal carbonyl by F. The only case of the absence of chemiluminescence in the case of the oxidation of Mn/sub 2/(CO)/sub 10/ is related to the existence of an Mn-Mn bond in this metal carbonyl. Mn/sub 2/(CO)/sub 10/ also efficiently quenches the background chemiluminescence due to the reaction of XeF/sub 2/ with CH/sub 2/Cl/sub 2/ and toluene.

Bright chemiluminescence upon the oxidation of organoaluminum compounds by xenon difluoride

Chemiluminescence was found in the reaction of XeF/sub 2/ with (C/sub 2/H/sub 5/)/sub 3/A1 (TEA), (i-C/sub 4/H/sub 9/)/sub 3/ X A1, (i-C/sub 4/H/sub 9/)/sub 2/A1H, and (C/sub 2/H/sub 5/)A1C1/sub 2/ in CH/sub 2/C1/sub 2/. The product composition indicates a redox reaction of XeF/sub 2/ with the A1-C bond. The kinetic curves for the chemiluminescence intensity which feature brightness maxima indicate luminescence excitation in reactions of unstable intermediates. Organoxenon compounds have been proposed for these intermediates.