G.A. Razuvaev

Oxidation of bis(triethylgermyl)mercury in the presence of tert-butyl alcohol

Abstract The oxidation of bis(triethylgermyl)mercury by oxygen in the presence of tert-butyl alcohol has been investigated. It has been shown that the dependence of the rate of oxidation on the value of n 1 for tert-butyl alcohol within the range n = 0–12 is similar to that for unassociated ligand-catalysts. On increasing n further (from 12 to 60) increasing association of the alcohol causes a drastic increase in the reaction rate relative to the increase in n due to the higher catalytic activity of the high molecular weight associated species.

The formation of a reversible complex between diethylcadmium and oxygen

Abstract From an investigation of the autoxidation of diethylcadmium (DEC) in n-heptane the formation of a reversible 1 2 DEC-oxygen complex has been established by a kinetic method. Some properties of this complex have been studied, viz. its ability to undergo spontaneous and catalytic transformation into bis(ethylperoxy)cadmium and its ultraviolet and infrared absorption spectra.

Oxidation of bis(triethylsilyl)mercury by oxygen in the presence of triphenylphosphine

Abstract It has been established that triphenylphosphine is an effective catalyst for the oxidation ofbis(triethylsilyl)mercury by oxygen. Some phenomenal features and the final products of oxidation are described, and the mechanism of oxidation is discussed.

Kinetics and mechanism of dimethylcadmium auto-oxidation in decane

Abstract The liquid-phase auto-oxidation of dimethylcadmium in n-decane has been investigated at 45–60°C. The process occurs by a chain free-radical mechanism, to give the auto-oxidation products MeOOCdMe and (MeOO) 2 Cd. The chain-initiation reaction has been studied by the inhibitor method. The rate of radical generation decreases with increasing oxygen concentration in the reaction mixture. The role of peroxide products in the auto-oxidation process has been clarified, and the probable mechanism of dimethylcadmium auto-oxidation is discussed.

The investigation of the bis(triethylgermyl) mercury oxidation with oxygen

Abstract The formal kinetics of auto-oxidation of bis(triethylgermyl) mercury liquid phase, and its oxidation in the presence of ammonia are investigated. The molecular character of the process and its catalysis by triethylgermyloxide, triphenylphosphine, triethylamine and ammonia are established. The mechanism of the auto-oxidation of bis(triethylgermyl) mercury is discussed.

Auto-oxidation of ethyl(triethylsilyl)mercury

Abstract The auto-oxidation of ethyl(triethylsilyl)mercury has been investigated. It has been established that auto-oxidation occurs through a free-radical chain process, initiation involving the decomposition of ethyl(triethylsilyl)mercury by means of a bimolecular mechanism with the formation of radicals. The reaction products have been identified and a mechanism is suggested.

The investigation of complexing organic derivatives of group IV and V elements with oxygen by electronic emission spectroscopy

Abstract Electronic emission spectra of phenyl derivatives (C6H5)3M (M = N, P, As, Sb, Bi), (C6H5)4M (M = C, Si, Ge, Sn, Pb), (C6H5)3MH (M = Si, Ge) and tetraalkylstannanes R4Sn (R = CH3, n-C4H9, n-C5H11) have been studied at 77 K. The process of phosphorescence quenching by dissolved oxygen is predominant among other deactivation processes of triplet states. The oxygen quenches phosphorescence with the formation of labile donor—acceptor complexes. The bimolecular quenching process obeys Stern—Volmer equation. It has been shown that the compounds investigated and oxygen have donor as well as acceptor properties when they form complexes. Donor—acceptor properties of these compounds depend strongly on n,π-conjugation, energy of π- and σ-bonds with participation of nd-orbitals for the elements of phosphorus and silicon subgroups and on steric factors.

On the influence of tris(triethylgermyl)stibine association on its oxidation by oxygen

Abstract It has been established that tris(triethylgermyl)stibine associates under the influence of temperature, light and in contact with triphenylphosphine or triethylamine. It is shown that association of tris(triethylgermyl)stibine leads to a change in the nature of the process of autooxidation from a chain free-radical (for monomeric forms) to one taking place without the participation of free radicals (for polyassociates). The yields and some phenomenal features of autooxidation of tris(triethylgermyl)stibine at different multiple associations are studied.

Molecular complexing as the initial stage of some reactions of organometallic compounds

Abstract Complexing of molecular oxygen with arylmercury compounds and phenyl derivatives of Group IV and V elements has been studied by electronic spectroscopy. The type of complexing appeared to depend on the nature of the central heteroatom in the organometallic compounds. The chemical model for the reaction of R 2 Hg (R = Et, n-Pr, n-Bu, Ph) with CCl 4 indicates that the complex R 2 Hg · L (L = molecular oxygen, aromatic compound) is formed in the initial stage of the interaction. By studying the influence of π-donors on this process the correlation between the yield of alkylmercuric chloride and the donor properties of the ligand has been determined.