Reaction of tetrafluorosilane with tris(2-hydroxyethyl)amine, tris(2-trimethylsiloxyethyl)amine and bis(2-trimethylsiloxyethyl)amine and its N-methyl derivative. 1,1-difluoroquasisilatranes

Reaction of tetrafluorosilane with tris(2-hydroxyethyl)-and tris(2-trimethylsiloxyethyl)amine results in formation of 1-fluorosilatrane and fluorosilatrane in 75 and 53% yield, respectively. Reaction of tetrafluorosilane with bis(2-trimethylsiloxyethyl)amine and its N-methyl derivative leads to the hitherto unknown 1,1-difluoroquasisilatranes (N → Si) F₂Si(OCH₂CH₂)₂NR (R = H, Me) containing donor-acceptor bond N → Si and pentacoordinate silicon atom. The structure of the synthesized compounds was proved by ¹H, ¹³C, ¹⁵N, ¹⁹F, ²⁹Si NMR and IR spectroscopy.     

AM1 studies of photoelectron spectra

Five ionization potentials for thesp,ac andsp, sp conformers of (acetylthiomethyl)trifluorosilane MeC(O)SCH₂SiE₃ and six ionization potentials for the same conformers of (benzoylthiomethyl)trifluorosilane PhC(O)CH₂SiF₃ were calculated by the semiempirical AM1 method. The resulting values are in good agreement with the data of photoelectron spectroscopy only for thesp.ac conformers. The structure of the preferred conformer of (acetylthiomethyl)trifluorosilane was confirmed by measurement of its dipole moment in the gas phase. The influence of the long-range inductive effect (field effect) on the energy of nonbonding electrons of the carbonyl oxygen atom in the series of acetic acid derivatives was observed. For Part 9, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 236–241, February, 1998.     

Divinyl Sulfoxide: XI. Selective Addition of Carbonodithioate Anions to Divinyl Sulfoxide in the Water-Benzene System

Selective monoaddition of carbonodithioate anions to divinyl sulfoxide gives rise to O-alkyl S-[2-(vinylsulfinyl)ethyl] carbonodithioates [ROC(S)SK, R = Et, Bu; 42–50°C, 6 h, NaHCO₃, aqueous benzene].     

The interactions of (=O→Si)-(benzoyloxymethyl)trifluoro-and -(benzoyloxymethyl) methyldifluorosilanes with a solvent

The IR spectra of solutions of (=OSi)-(benzoyloxymethyl)trifluorosilane (1),-(benzoyloxymethyl)methyldifluorosilane (2), and butyl benzoate (3) are examined in the region of thev(C=O) stretching vibrations in 24 solvents. The ability of compounds1—3 to undergo specific intermolecular interactions is evaluated from the dependence ofv(C=O) on the Kamlet-Taft (^*,, ) parameters, which was obtained for the carbonyl groups involved in the intramolecular coordinate (=OSi) bond and for free carbonyl groups. The corresponding values of the coefficients in the Kamlet-Taft equations are indicative of a weak ability of pentacoordinate silicon compounds1 and2 to undergo acid-base interactions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 689–692, April, 1995.     

IR spectroscopic study of substituent effects in N,N-dimethylhydrazides of aromatic acids

Conclusions An IR spectroscopic study showed that the C=0 values in the spectra of N,N-dimethylhydrazides of aromatic acids, RCONHN(Me)₂, correlate linearly with a regression equation obtained for the unsubstituted hydrazides of aromatic acids, RCONHNH₂. This dependence differs significantly from that for N-methyl-N-aroylhydrazines, in which ,-conjugation in the RC(O)N group is more pronounced.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2353–2355, October, 1987.     

Reactions of 1-Allenylpyrazole and 1-Allenyl-1,2,4-triazole with Hydrogen Chloride and Metal Chlorides

1-Allenylpyrazole and 1-allenyl-1,2,4-triazole react with hydrogen chloride via proton addition at the pyridine-like nitrogen atom (N² and N⁴, respectively). In the reaction with 1-allenylpyrazole, 1-[(E)-3-chloro-1-propenyl]pyrazole is also formed via regio- and stereoselective addition of hydrogen chloride to the propadienyl group. 1-Allenylpyrazole and 1-allenyl-1,2,4-triazole act as unidentate ligands with respect to Co, Ni, Cu, Zn, Cd, Pd, and Sn, the donor centers being N² and N⁴, respectively. Apart from mononuclear coordination compounds, 1-allenylpyrazole gives rise to polymeric complexes which contain units and blocks formed by the free ligand.     

Spectroscopic study of germanium-containing compounds

Conclusions The values of C=0 in the IR spectra and the position of the band from the n ^* electronic transition in the UV spectra of the amides R¹CONR²R³ vary linearly with the inductive effect of the R¹ substituent (for R²=R³=H, Alk). This may indicate the absence of the intramolecular coordination Ge 0, where or. The substituent R¹=Ge(C₂H₅)₂ exhibits electron-acceptor properties besides a +I-effect.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 349–352, February, 1984.