NMR spectra and isotope analysis of hexaethyldistannane

The ¹³C-{¹H} and ¹¹⁹Sn-{¹H} NMR spectra of hexaethyldistannane were measured and analyzed using an iteration program for the calculation of the complete line shape with correction of a residual inhomogeneity of the magnetic field and phase distortions. Signals of 22 isotopomers containing magnetic isotopes of tin and carbon in different pairwise and triple combinations were identified, and their spectral parameters were determined. The content of isotopes ¹¹⁹Sn, ¹¹⁷Sn, and ¹¹⁵Sn in the molecule was determined with a high accuracy sufficient for the study of isotope effects in chemical reactions.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2102–2104, October, 2004.     

Electroreduction of a Binuclear Macrocyclic Complex of Copper(II) of the Robson Type in Aqueous Solutions

The electroreduction of a binuclear complex of copper(II) with a macrocyclic Schiff base of the Robson type on the basis of 4-tert-butyl-2,6-diformylphenol and 1,3-diaminopropane on the dropping-mercury, gold, amalgamated-gold, and glassy-carbon electrodes is studied in an aqueous environment. The data of experiments on preparative electrolysis and the results of measurements by a method of cyclic voltammetry and classic polarography suggest that the complex under study undergoes reduction in an aqueous environment with the transfer of four electrons with formation of copper(0) and a free Schiff base, which in conditions under investigation experiences hydrolytic decomposition.     

DFT modeling of the first step of plastoquinol oxidation by the iron–sulfur protein of the cytochrome b6f complex

1. Download high-res image (126KB)
2. Download full-size image

     

Heteroorganic betaines

The [Ph₃P⁺−CMe₂−SiMe₂−SEt]Br⁻ salt was prepared by the reaction of betaine Ph₃P⁺−CMe₂SiMeR−S⁻ (1a: R=Me) with EtBr. Acetylation of betaine1a or Et₃P⁺−CHMeSiMe₂−S⁻ (2a) afforded 2,2,6-trimethyl-1,3-dioxa-2-silacyclohex-5-ene-4-thione      

Heteroorganic betaines

Photolysis and thermal decomposition of betaines R₃P−CR¹R²−SiR³R⁴−S⁻ (1) follows two main pathways: (a) a Corey—Chaykovsky type reaction with elimination of Ph₃P and generation of silathiirane (2) and (b) a retro-Wittig type reaction accompanied by elimination of R₃P=CR¹R² and generation of silanethione R³R⁴Si=S (3). Highly reactive compounds2 and3 undergo subsequent transformations to give derivatives of tetrahydro-1,4-dithia-2,5-disilin, 1,3-dithia-2,4-disilolane, and phosphonium salts ofsymm-tetraorganodisilthiane dithiolates [Ph₃P⁺CHR¹R²]₂[(R³R⁴SiS⁻)₂S]. The structures of the compounds obtained were established by X-ray diffraction analysis and multinuclear NMR spectroscopy. For part 3, see Ref. 1. The betaines Et₃P⁺CHMeSiMe₂S⁻ and Et₃P⁺CHMeSiPh₂S⁻ with alkyl groups at the phosphorus atom are distinguished by high thermal stability; their spectral characteristics do not change during storage of solutions of these compounds in pyridine-d₅ or metastable solutions in benzene-d₆ for 1–2 years at −20°C in sealed evacuated tubes or on heating (150°C) for 15 h. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1594–1603, September, 2000.     

A new method for generating organosilanones

A new method for the generation of organosilanones by the reaction of betaines, R₃P⁺-CR¹R²-SiR³R⁴-S^–, with (Et₃Sn)₂O was suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2246–2247, December, 1994.This study was financially supported by the Russian Foundation for Basic Research, Project No. 94-03-09710.     

Electron-transfer induced change of direction of interannular haptotropic isomerization of fluorenyltricarbonylchromium anions

It has been shown by cyclic voltammetry in a THF medium in the temperature range from –70 °C to +20 °C that one-electron electrochemical reduction of (⁶-C¹³H¹⁰)Cr(CO)₃ (1) to the corresponding 19-electron anion radical (1 ^–) is accompanied by splitting off of a H atom to form the 18-electron carbon-centered anion (⁶-C₁₃H₉)Cr(CO)₃ (^–2 ), which at room temperature undergoes intramolecular haptotropic isomerization to the metal-centered (⁵-C₁₃H₉)Cr(CO)₃ ^– (^– 3) anion. The reversible one-electron reduction of3 ^– to the corresponding 19-electron radical dianion3 ^2.– induces ^{5 6} interannular isomerization. In contrast to the equilibrium shift to the ⁵-isomer in 18-electron complexes 2 and 3, in their 19-electron analogs the equilibrium is shifted to the ⁶-isomer.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–53, January, 1994.This work was carried out with financial support from the Russian Foundation for Basic Research (no. 93-03-5209)     

Reactions of triferrocenylchloromethane hydrochloride

Conclusions Triferrocenylchloromethane hydrochloride reacts with nucleophilic reagents (organomagnesium and-sodium compounds, aluminum lithium hydride, sodium methylate, sodium cyanide) to yield the corresponding triferrocenylmethane derivatives.