Structure of N-(1-silatranylmethyl) and N-(trimethoxysilyl-methyl) derivatives of nitrogen-containing heterocycles according to data of NMR, IR, and UV spectroscopy

The ¹H, ¹³C, ¹⁵N, and ²⁹Si NMR, IR, and UV spectra of N-(1-silatranylmethyl) and N-(trimethoxysilylmethyl) derivatives of nitrogen heterocycles have been studied. The dependence and interrelation of the chemical shifts of ²⁹Si and ¹⁵N nuclei of the silatranyl group in the spectra of N-(1-silatranylmethyl)-substituted nitrogen heterocycles are determined by the nature of the heterocyclic system. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1857–1865, December, 2006.     

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.     

Hydrosilylation of N-allylpyrrolidine and N-allylpiperidine

It was found that the hydrosilylation of N-allylpyrrolidine and N-allylpiperidlne by trialkylsilanes, triethoxysilane, and 3H-heptamethyltrisiloxane in the presence of H₂PtCl₆ · 6H₂O proceeds to form -adducts.Communication XXXII from the series Nitrogen-Containing Organosilicon Compounds. See [1] for communication XXXI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 485–487, April, 1972.     

Synthesis and Structure of 1- and 2-Isomers of (Trimethoxysilylmethyl) and (Silatranylmethyl)benzotriazole

We have synthesized 1- and 2-(trimethylsilylmethyl)- and 1- and 2-(trimethoxysilylmethyl)benzotriazoles by reaction of 1,2,3-benzotriazolylsodium with trimethyl- or trimethoxy(chloromethyl)silane. We obtained 1- and 2-(silatranylmethyl)benzotriazoles by transesterification of the latter with triethanolamine.     

3,3-Dimethyl-2,3,5,6-tetrahydroimidazo[2,1-b][1,3,4]thiazasilole and Its Derivatives with Five-Coordinate Silicon Atom

Previously unknown 3,3-dimethyl-2,3,5,6-tetrahydroimidazo[2,1-b][1,3,4]thiazasilole and its zwitterionic derivatives containing five-coordinate silicon atom, namely 7-substituted 3,3-dimethyl-2,3,5,6-tetrahydroimidazo[2,1-b][1,3,4]thiazasilol-4-ium chlorides, have been synthesized by reaction of 1,3-bis(trimethylsilyl)tetrahydroimidazole-2-thione with chloro(chloromethyl)dimethylsilane and subsequent transformations of the products.     

Electronic interaction between the nitrogen,oxygen, and silicon atoms in the molecules of α-aziridin-1-ylalkoxy(triethyl)silanes

By the PMR method we have established the existence of a high frequency of the inversion of the nitrogen atom in the molecules of -aziridin-1-ylalkoxysilanes. This is due to the fact that the high (because of p-d bonding with the silicon atom) electronegativity of the oxygen atom in the Si-O-C-N system makes possible an interaction between the unshared electron pair of the nitrogen atom and the antibonding orbital of the C-O bond. The latter, in its turn, increases the degree of p-d bonding between the oxygen and silicon atoms (in these compounds the order of the Si-O bond is greater than in the alkoxysilanes).     

29Si NMR spectroscopy of cyclosiloxanes

Journal of Structural Chemistry -