Experimental and theoretical study on the structure and reactions of 1-methoxypropane radical cations

Structure and mechanism of thermal and photochemical reactions of radical cations of methyl n-propyl ether (MPE) were studied in irradiated freonic matrices CFCl₃, CF₂ClCFCl₂, and CF₃CCl₃ at 77 K. The quantum chemical calculations of the structure of radical cations and products of their transformations were carried out with methods based on the density functional theory (DFT). Experimental and calculation results show that the MPE radical cations are characterized by substantial delocalization of spin density to the propyl group. The action of light on the MPE radical cations in a CF₃CCl₃ matrix at 77 K results in intramolecular rearrangement yielding the distonic radical cation ^.CH₂CH₂CH₂(OH⁺)CH₃. It was found that the primary MPE radical cations underwent irreversible transformation to CH₃CH₂CH₂OCH ₂ ^. radical as a result of an ion-molecule reaction that occurred in a CF₂ClCFCl₂ matrix upon heating the sample to 110–120 K or in a CFCl₃ matrix upon increasing the solute concentration.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 2, 2005, pp. 105–113.Original Russian Text Copyright © 2005 by Belevskii, Feldman, Tyurin.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis,crystal structures,and electrochemistry of Cu<Superscript>II</Superscript> complexes with tetradentate N<Subscript>2</Subscript>O<Subscript>2</Subscript> ligands derived from 3,7-diazabicyclo[3.3.1]nonan-9-one

New copper(II) complexes with tetradentate ligands derived from 1,5-diphenyl-3,7-diazabicyclo[3.3.1]nonan-9-one and containing the N,N′-2-hydroxyethyl, 2-methoxyethyl, and carboxymethyl substituents were synthesized. The crystal structures of the complexes were established and the complexes were studied by cyclic voltammetry. The ligands are preorganized for complexation and are highly complementary for a divalent copper cation. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1773–1782, August, 2005.     

Oxidative transformations of peridazines

Reactions of peridazines (1H-1,2-diazaphenalenes) with electron-donor reagents (quinones, potassium ferrocyanide) involve multistage oxidative transformations resulting in products of dimarization and (or) dehydration.     

CHF3…H2O complex revisited: a matrix isolation and ab initio study

Structural Chemistry - The structural and spectroscopic features of the CHF3…H2O complex have been investigated using high-level ab initio calculations and IR matrix isolation spectroscopy....     

A Speckle Interferometric Flame Research Technique

Technical Physics - Methods of recording and automated processing of the results of phase-modulated speckle interferometry of optically dense (opaque to intrinsic radiation) flames containing a...     

Ionizing radiation-stimulated diffusion and desorption of hydrogen from metals

The processes of hydrogen diffusion from a sample depth activated by electrons with an energy of tens of keV are studied. The difference from the known models of electron-stimulated desorption, which consider as a rule electron energies from 0.5 to several keV, is noted. The proposed model is shown to correspond to at least two established experimental facts: the nonlinear dependence of hydrogen isotope desorption on the electron beam current density affecting the sample and the dependence of hydrogen desorption on the irradiation time of the sample.     

Isotope distribution in electrochemical ion implantation in metals and composite materials

Experimental data are reported for the isotope distribution in the electrochemical implantation of lithium and hydrogen isotopes in metals and composite materials from LiOD and LiOH solutions. General regularities are identified for the changes in isotopic composition in the metal-matrix in which ions are implanted, in impurities in the metals, and in the ions responsible for electrolyte conductivity. Possible mechanisms for lithium implantation are considered on the basis of the analysis of isotope distribution.     

Synthesis of 4,8-Dibenzoyl-1,5-dihydroxynaphthalene and of Some Derivatives Thereof

Demethylation of 4,8-dibenzoyl-1,5-dimethoxynaphthalene was carried out to afford the corresponding bis-peri-hydroxydiketone and its derivatives. The acylation and alkylation was performed with one among these derivatives, 6-benzoyl-2-phenylnaphtho[bc]furan-5-one.     

Influence of a Hydrogen Atmosphere on the Properties of an Aluminum Oxide Film on VT1-0 Titanium

Technical Physics - In this study, we have considered interaction between an aluminum oxide film magnetron-sputtered on commercially pure VT1-0 titanium and a hydrogen atmosphere. The time the...