A series of anionic phenylsilicon(IV) bis-catecholate complexes, where (Cat1)– = catecholate, (Cat2)– = 3,4,5,6-tetrabromocatecholate, (Cat3)– = 4-cyanocatecholate, (Cat4)– = 4-nitrocatecholate, (Cat5)– = 3-fluorocatecholate, and (Cat6)– = 4,5-dibromocatecholate, were prepared by the reaction of trimethoxyphenylsilane with two equivalents of catechol or its derivatives containing electron-withdrawing substituents in the benzene ring in the presence of dicyclohexylamine. The complexes were characterized by IR spectra and 1H, 13C, and 29Si NMR spectra, voltammetry, and ESR. The heteroligand anionic phenylsilicon(IV) complexes crystallized from solutions as salts (Chex2NH2)[PhSi(Cat1)2] (I), (Chex2NH2)-[PhSi(Cat2)2]·0.5C6H14 (II), (Chex2NH2)[PhSi(Cat3)2]·2C6H6 (III), (Chex2NH2)[PhSi(Cat4)2]· H2O (IV), (Chex2NH2)[PhSi(Cat5)2] (V), and (Chex2NH2)[PhSi(Cat6)2] (VI) (Chex2 $${\text{NH}}_{2}^{ + }$$ = dicyclohexylammonium). The composition and structure of the products were confirmed by X-ray diffraction data (CCDC nos. 2150293–2150297 for I–V, respectively). The effect of substituent in the benzene ring on the electronic structure of the anion was studied by PBE0/6-311G(d,p) quantum chemical calculations with allowance for non-specific solvation (PCM model). The oxidation potentials of II–VI were measured; radical formation upon electrochemical oxidation and reduction was observed for II.

This review is devoted to the scientific achievements of the departments of organic chemistry in higher schools of Russia within the past decade.

The review describes the history of development of organic chemistry in higher schools of Russia over a period of 170 years, since the emergence of organic chemistry in our country till now.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Hydrolysis of monochelate five-coordinate chlorosilanes MeC(O)N(Me)CH2SiMe2Cl (Ia), L7CH2SiMe2Cl (Ib), L8CH2SiMe2Cl (Ic), PhtImCH2SiMe2Cl (Id), MeC(O)N(Me)CH2SiMePhCl (IIa), and Im5CH2SiMePhCl (IIe), containing a monoanionic C,O-chelating ligand LCH2 [L is an amide, n-membered lactam (L n ), imide (Im n ), or phthalimide (PhtIm) residue]. The structures of the starting chlorides and their hydrolysis products were established by means of X-ray diffraction analysis. Based on experimental and published data, a general scheme of hydrolysis of mono-C,O-chelate chlorosilanes was suggested, including initial formation of silyloxonium chlorides III and subsequent formation of disiloxane dihydrochlorides IV.

Cationic O→Si-coordinated bis-C,O-chelate silicon complexes [(LCH2)2Si(F)]BF4, containing monoanionic AcN(Me)CH2, 2-oxoperhydroazepinomethyl, 2,2-dimethyl-4-oxobenzo[1,3]oxazin-3-ylmethyl, and 4-methyl-2-oxoquinolinomethyl C,O-coordinating ligands were synthesized by the reaction of trimethylsilyl derivatives of amides, lactams, and related compounds with (ClCH2)2SiCl2 in a 2:1 ratio. The synthesized complexes were reacted with KF to obtain six-coordinate bis-C,O-chelates [(LCH2)2SiF2] which were then converted into the starting tetrafluoroborates by treatment with BF3·Et2O. First representatives of cationic bis-O,O′-chelate silicon complexes with a 2-hydroxyacid amide fragment {XSi[OCH(R)C(O)NMe2]2}Y (X = Cl, Me, t-Bu, Ph, BrCH2; R = H, Me; Y - Cl−, ClHCl−, HgBr 3 − ) were synthesized by the reaction of XSiCl3 with O→SiMe3 derivatives of dimethylamides of (S)-lactic and glycolic acids in a 1:2 ratio or by transesterification of XSi(OMe)3 with glycolic acid dimethylamide followed by addition of acetyl bromide (ratio 1:3:1). The structure of the resulting chelates was proved by X-ray diffraction analysis.

The effect was revealed of activation of the siloxane bond in lactams derived from 1,1,3,3-tetramethyl-1,3-disiloxanes containing a C(O)NCH2SiOSi fragment in reactions with electrophilic reagents, leading, in the general case, to facile Si-O bond cleavage and formation of five-coordinate silicon chelate rings incorporating the lactam oxygen atom which forms the coordination bond O-->Si. The structure of 1,1,3,3-tetramethyl-1,3-bis[N-(1-phenylethyl)]acetamidomethyl]-1,3-disiloxane and the adduct of 1,1,3,3-tetramethyl-1,3-bis(2-oxopyrrolidinomethyl)-1,3-disiloxane with trichloroacetic acid was studied by X-ray diffraction. For the first time in siloxanes with amidomethyl and related substituents at the silicon atom in the former compound there was found a weak coordination interaction O . . . Si (2.8 Angstrom).

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.