E. N. Sinotova

Radiochemical Study of Gas-Phase Reactions of Nucleogenic Diethylgermyl Cations with Dibutyl Ether and 1-Butanol

Reactions of tritium-labeled free diethylgermyl cations with dibutyl ether and 1-butanol in a gas phase were studied by the radiochemical method. Mechanisms of the corresponding ion-molecular reactions were suggested, and the most probable paths of the cation (C2H5)2TGe+ conversion into other isomeric forms were shown.

Synthesis of phenylsilocane tritium-labeled at the benzene ring

A strategy for synthesis of the 2-phenyl-2-hydro-1,3-oxa-6-aza-2-silacyclooctane doubly tritium-labeled (2,4- or 2,6-) at the benzene ring has been elaborated. The products are sources of the silyl cations having the atrane structure.

Synthesis of diethylditritiumstannane Et2SnT2, a generator of stannylium cations

In recent decades tricoordinated cations of heavy elements of the 14-th group of the Periodic table, R3M (M = Si, Ge, Sn) are objects of intense study [1–4]. Despite the fact that the existence of R3M cations in gas phase was proved convincingly, their identification in the condensed phase remains a challenge. This is due to the unique ability of the heavy elements of 14th group to expand their coordination sphere in the reactions with the nucleophiles of any kind. Recent progress in this area relates to the development of the chemistry of anions with extremely low nucleophilicity, such as carborane anion [CB11X12], X = halogen, H [5], borane dianion [B12X12], X = Cl, Br [6], perfluorotetraalkylborates [B(C6F4X)4], X = F, SiR3 [7]. Use of such anions, solvents with low nucleophilicity, and suitable methods of generating allowed, finally, to synthesize and characterize some tricoordinated cations R3M. So, the tin cations of low coordination were obtained in two ways: by splitting a Sn–C bond in tetraorganylstannanes [8] and by the addition of an R cation to stannylene [9]. cations. The method is based on the use of the processes of tritium β-decay in the tritium-labeled stannanes.

Nucleogenic tricoordinated cations of the 14th group elements

The interaction of tricoordinated cations of the 14th group elements generated by the nuclear chemical method with representatives of π-(aryls, olefins) and n-electron-donating (alcohols, ethers) compounds was studied. A comparative analysis of these interactions was carried out on the basis of the results obtained and revealed the differences in the reaction mechanisms of the carbenium ion compounds and mezoid cations. No drastic differences in the behavior of silylium and germylium cations was observed. The possibility of isomerization of the mezoid cations to donor-acceptor complexes of the [HM+·H2] type was experimentally shown for the first time for dimethylgermylium cations taken as an example. The quantum chemical calculations of the studied cations and adducts of their interactions in terms of the functional density theory prove the reaction mechanisms proposed.

Radiochemical Investigation of the Interaction of Nucleogenic Diethylgermylium Ions with Methyl tert-Butyl Ether

Radiochemical method was used in the study of the interaction of free diethylgermylium cations with methyl tert-butyl ether in the gas and condensed phases, and the mechanisms of the relevant ion-molecular reactions were proposed. The most probable pathways of the (C2H5)2TGe+ cation transformation into other isomeric forms are shown as a result of B3LYP calculation with cc-pVTZ basis set.

A radiochemical study of isomerization of dimethylgermylium ion, with the reaction of Me2HGe+ cation with methyl tert-butyl ether as example

The reaction of dimethylgermyliumion with methyl tertbutyl ether in the gas phase was studied by the radiochemical method, and the mechanisms of the corresponding ion—molecule reactions were suggested. The possibility of the existence of germyliumions generated by the nuclear-chemical method was proved by the example of dimethylgermylium ion. Possible pathways of transformation of (CH3)2HGe+ cation into other isomeric forms were analyzed by B3LYP calculations with 6-31G* and aug-cc-pVDZ basis sets.

Radiochemical study of gas-phase reactions of diethylstannilium cations Et2SnT+ with oxygen-containing compounds: I. Interaction of diethylstannilium cations with methyl tert-butyl ether

Radiochemical method was applied to study the gas-phase interaction between the nucleogenic diethylstannyl cations Et2SnT+ and methyl tert-butyl ether. The possible reaction mechanisms are considered. Diethylstannylium cations are found to isomerize during the reaction to tertiary cation Me2EtSn+, as well as undergo a rearrangement accompanied by elimination of ethane rater than ethylene, in contrast to the cases of silicon and germilium analogs.

Radiochemical study of interaction of the nucleogenic diethylgermylium cations with benzene in the gas and condensed phases

Interaction of free diethylgermylium ions with benzene in the gas and condensed phases was studied by the radiochemical method. A possible mechanism of the ion-molecular reactions was suggested. At the interaction of these ions with benzene the products of germylation of the latter were not detected. More advantageous are the processes of degermylation leading to the formation of tritium-labeled benzene. A possibility of rearrangement of the nucleogenic diethylgermylium cation into other isomeric forms was revealed, these forms were calculated by B3LYP method with the 6–31G* and cc-pVTZ basis sets.

Germanium analogs of carbenium ions

The review summarizes advances in the production of germanium analogs of carbenium ions both per se in solutions and crystals and as intermediates in reactions of organogermanium compounds. The data on the structures of germylium cations of different types are considered. Emphasis is given to the reactivity of germylium ions and their ion-molecule reactions with nucleophilic reagents in the gas and condensed phases.

Radiochemical study of gas-phase reactions of diethylstannyl cations Et2SnT+ with oxygen-containing compounds: II. Reaction of diethylstannyl cations with butanol

Gas-phase reaction of nucleogenic diethylstannyl cations Et2SnT+ with butan-1-ol has been studied by the radiochemcal method, and probable reaction mechanisms have been proposed. During the process diethylstannyl cations undergo isomerization into tertiary Me2EtSn+ cations and rearrangement with elimination of ethane. Thermochemical parameters of reactions of diethyl-substituted cations derived from Group 14 elements (Et2TM+; M = C, Si, Ge, Sn) with alcohols have been analyzed by the M06L aug-cc-pVDZ quantum chemical method.