O. M. Trofimova

Reaction of phenyltrifluorosilane and phenyl(hydrocarbyl)difluorosilanes with bis(2-hydroxyethyl)-and tris(2-hydroxyethyl)amine and their N-methyl and O-trimethylsilyl derivatives. A novel route to quasisilatranes

Reaction of phenyltrifluorosilane, diphenyldifluorosilane, and methylphenyldifluorosilane with bis(2-hydroxyethyl)amine, methyl-bis(2-hydroxyethyl)amine, methyl-bis(2-trimethylsiloxyethyl)amine, leads to 1,3-dioxa-6-aza-2-silacyclooctane derivatives, (N → Si) quasisilatranes: 1,1-difluoroquasisilatrane, 1-phenyl-1-fluoro-5-methylquasisilatrane, or 1-methyl-1-fluoroquasisilatrane, containing the donor-acceptor bond N → Si and pentacoordinate silicon atom. 1-Phenylsilatrane was found to be the product of the reaction of phenyltrifluorosilane with tris(2-trimethylsiloxyethyl)amine, whereas with tris(2-hydroxyethyl)amine 1-phenylsilatrane and 1-fluorosilatrane were formed in the molar ratio of 3:1. The structure of the synthesized compounds was proved by 1H, 13C, 15N, 19F, 29Si NMR and IR spectroscopy.

The unusual reaction of phenyltrifluorosilane with 2-aminoethanol and its N-methyl derivatives

139 In the course of study of the C–Si bond cleavage in phenyltrifluorosilane (PTS) with the aim of using PTS in the synthesis of organoelement compounds [1–6], we studied the reaction of PTS with 2-aminoethanol and its Nmethyland N , N -dimethyl derivatives. Previously, we found that the reaction of protodesilylation of PTS with 8-hydroxyquinoline or 8-mercaptoquinoline leads to new intracomplex heterocyclic compounds, (N Si) 8-(trifluorosiloxy)quinoline or (N Si) 8-(trifluorosilylthio)quinoline, containing a pentacoordinated silicon atom [3] (reaction 1): (1)

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.

Synthesis and UV spectra of 8-mercaptoquinoline organosilicon derivatives and their metal halides complexes

Abstract IR and UV spectra of (8-quinolylthiomethyl)trimethylsilane ( 1 ), -trimethoxysilane ( 2 ), -silatrane ( 3 ) and their complexes with CuCl 2 , ZnCl 2 , PtCl 2 and SnCl 4 in MeCN have been studied. The UV spectra of 8-methylthioquinoline, its HN + cation and HN + , HS + dication were calculated at the AM1 (CI) level. It was shown that 1 ·PtCl 2 , 2 ·ZnCl 2 and 3 ·ZnCl 2 are chelates. The 2 ·SnCl 4 and 3 ·SnCl 4 compounds have a strong N→Sn bond. The 2 ·CuCl 2 and 3 ·CuCl 2 complexes are a mixture of coordination compounds having N→Cu or N→Cu←S bonds.

N-Silatranylmethyl Derivatives of Pyrrole, Indole, and Carbazole

Organosilicon derivatives of pyrrole, indole, carbazole, and 2-methylindole containing (MeO)3SiCH2, Et3SiCH2, or N(CH2CH2O)3SiCH2 group on the nitrogen atom were synthesized. Their structure and stereoelectronic parameters were studied by X-ray diffraction, 1H, 13C, 15N, and 29Si NMR, IR and UV spectroscopy, and dielcometry, as well as by quantum-chemical calculations.

Unusual crystal and molecular structure of the 1-(1-silatranylmethyl)-3,5-dimethylpyrazole complex with zinc dichloride

The crystal and molecular structure of a 1-(1-silatranylmethyl)-3,5-dimethylpyrazole complex with zinc dichloride (I) is determined by XRD. The coordination polyhedron of the zinc atom is a tetrahedron formed by two covalent Zn-Cl bonds and coordination Zn ← N and Zn ← O bonds. Compound I is the first example of how an endocyclic oxygen atom of the silatranyl fragment participates in the coordination of the metal atom with the formation of a six-membered heterocycle.

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.

Crystal and molecular structure of the complex of 2-(1-silatranylmethylthio)-4,5-benzo-1,3-thiazole with CoCl2 and MeCN

The crystal and molecular structure of the complex of 2-(1-silatranylmethylthio)-4,5-benzo-1,3-thiazole with CoCl2 and MeCN (I) is determined by single crystal X-ray diffraction. The geometry of the silatranylmethyl moiety in complex I is compared to the geometry of 1-(2′-benzthiazolylthiomethyl) silatrane. Molecular packing in the crystal is analyzed.

Synthesis and structure of (C=O→Si←O′=C′)bis(2-methyl-4-oxopyran-3-yloxy)difluoro-(λ6)siliconium

A new six-coordinate silicon compound, (C=O→Si←O′=C′)bis(2-methyl-4-oxopyran-3-yloxy)-difluoro(λ6)siliconium, containing two five-membered rings closed by C=O→Si coordination bonds, forms o protodesilylation trifluoro(phenyl)silane with 3-hydroxy-2-methylpyran-4-one (maltol). According to multinuclear NMR and IR spectral data and quantum-chemical calculations, the silicon atom in this compound has an octahedral environment with two cis-arranged C=O→Si bonds

Synthesis and molecular structure of 1-(2-pyridyloxy)silatrane

Abstract1-(2-Pyridyloxy)silatrane was synthesized by trans-etherification of 1-ethoxysilatrane with 2-hydroxypyridine as well as by the reaction of the latter with tetraethoxysilane and triethanolamine. Its structure was established by the XRD analysis of a single crystal, and in solution using the methods of 1H, 13C, 29Si NMR and IR spectroscopy.