Crystal structure of organosilicon compounds. XLVII. 1-(chlorodimethylsilylmethyl)-2-piperidone

Macharashvili, A. A.; Baukov, Yu. I.; Крамарова, E. П.; Oleneva, G. I.; Pestunovich, V. A.; Struchkov, Yu. T.; Shklover, V. E.

doi:10.1007/bf00752058

Cited by 10 publications

(17 citation statements)

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“…This behaviour is generally reflected by quantum-chemical studies of compounds 1-8 and these results augment the study of halides and triflate of 1-(dimethylsilylmethyl)piperidone-2 that we have previously published [28][29][30].…”

Section: Quantum-chemical Calculationsmentioning

confidence: 69%

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Negrebetsky

Taylor

Крамарова

et al. 2006

Journal of Organometallic Chemistry

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Section: Quantum-chemical Calculationsmentioning

confidence: 69%

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Negrebetsky

Taylor

Крамарова

et al. 2006

Journal of Organometallic Chemistry

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“…It also is of interest to compare axial bond distances in a series of chlorosilanes − that exist as trigonal bipyramids as a result of oxygen donor action. As the Si−O ax donor coordination increases, as judged by a progressive decrease in the associated Si−O ax distance from 2.43 to 1.92 Å, the Si−Cl ax distance increases from 2.15 to 2.35 Å, respectively.…”

Section: Resultsmentioning

confidence: 99%

Hexacoordination via Sulfur Donor Action in Nitrogen and Chlorine Bonded Bicyclic Tetraoxyphosphoranes¹

et al. 1997

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Oxidative addition reactions of a quinone with the sulfur containing cyclic chlorophosphine S[(t-Bu)MeC6H2O]2PCl (1) yielded the new bicyclic tetraoxyphosphoranes, S[(t-Bu)MeC6H2O]2PCl(O2C6Cl4) (2) and S[(t-Bu)MeC6H2O]2PCl(O2C14H8) (5). Further new derivatives of this class were prepared by chlorine displacement reactions of 2 and 5 to give S[(t-Bu)MeC6H2O]2P(NHC6H4Me)(O2C6Cl4) (3), S[(t-Bu)MeC6H2O]2P(NMe2)(O2C6Cl4) (4), S[(t-Bu)MeC6H2O]2P(NHCH2C6H5)(O2C14H8) (6), and S[(t-Bu)MeC6H2O]2P(NMe2)(O2C14H8) (7). X-ray studies of 2−6 revealed hexacoordination due to donor action by sulfur which is present as part of an eight-membered ring system. The series 2−6 formed geometries that were displaced along a coordinate from a square pyramid to an octahedron, ranging from 24% to 71%. The respective P−S distance decreased along this series from 3.04 to 2.48 Å as the octahedral character increased. Increased 31P NMR shielding accompanied the chloro derivatives 2 and 5, while increased π P−N back-bonding resulted in the least shielded members 4, 6, and 7 containing the less electronegative nitrogen atom. These changes in 31P chemical shift correlate with the extent of octahedral character where the more shielded phosphorus atom has the greater octahedral character. The analysis allows a lower limit in the phosphorus atom electrophilicity to be established that will allow hexacoordination in this series of bicyclic tetraoxyphosphoranes provided by a variation in ligand properties.

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“…Comparison of the geometric parameters of the hypervalent O6Si3Cl bond in compound IIb and related imidomethylsilyl (IV), amidomethylsilyl (V) and lactamomethylsilyl (VIa3VIc) derivatives of fivecoordinate silicon (Table 5) [5,12315] allows us to reveal the following trends.…”

mentioning

confidence: 98%

“…At the same time, the Si3Cl bond in five-coordinate silicon derivatives is more reactive than in four-coordinate in SNSi reactions [2]. The most important factor that determines the possibility of spontaneous substitution at the trigonal bipyramidal Si atom in reactions with trimethylsilyl derivatives Me 3 SiY is formation of a compound with a stronger O6Si coordination bond [3].It was previously established that the N,N-bis-(acetyl)aminomethyl ligand, like amidomethyl [4] and lactamomethyl [5,6], exhibits chelating ability. Proceeding with this research, we prepared N-chlorodimethylsilyl derivatives of 5-and 6-membered cyclic imides of dicarboxylic acids and studied the effect of the size of the imide ring on the strength of O6Si coordination.…”

mentioning

confidence: 99%

“…It was previously established that the N,N-bis-(acetyl)aminomethyl ligand, like amidomethyl [4] and lactamomethyl [5,6], exhibits chelating ability. Proceeding with this research, we prepared N-chlorodimethylsilyl derivatives of 5-and 6-membered cyclic imides of dicarboxylic acids and studied the effect of the size of the imide ring on the strength of O6Si coordination.…”

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confidence: 99%

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Synthesis, structure, and spatial arrangement of Si-substituted N-(dimethylsilylmethyl)imides

et al. 2004

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The synthesis of N- (chlorodimethylsilylmethyl)succinimide and N-(chlorodimethylsilylmethyl)-glutarimide by the reaction of the corresponding N-trimethylsilylimides with chlorodimethylsilane and by the reaction of unsubstituted imides with a mixture of hexamethyldisilazane with dimethylchloromethylchlorosilane is described. The formation of N-(chlorodimethylsilylmethyl)succinimide is followed by substitution by the silicon atom, which, depending on the reagent ratio, provides N-(dimethylsuccinimidomethyl)succinimide as the major or minor product. 1 H, 13 C, and 29 Si NMR spectroscopy and X-ray diffraction analysis showed that the silicon atom in N-(chlorodimethylsilylmethyl)glutarimide is five-coordinate. By contrast, in N-(chlorodimethylsilylmethyl)succinimide and N-(dimethylsuccinimidomethyl)succinimide, according to NMR and X-ray diffraction data, the silicon atom is four-coordinate. Quantumchemical calculations by the AM1 method show that the molecular conformations of N-(chlorodimethylsilylmethyl)imides containing an intramolecular O6Si bond are not energetically most favorable in the gas phase.One of the lines of our research on specific structural features of (O3Si) chelate compounds of fivecoordinate silicon is elucidation of the effect of substituents on the C and Si atoms on the strength of C=O6Si coordination and activity in substitution reactions at the silicon atom [1]. In the case of ligands containing bidentate lactamomethyl fragments, the strength of O6Si coordination, all conditions being equal, increases in going from five-to six-and sevenmembered lactam derivatives. At the same time, the Si3Cl bond in five-coordinate silicon derivatives is more reactive than in four-coordinate in SNSi reactions [2]. The most important factor that determines the possibility of spontaneous substitution at the trigonal bipyramidal Si atom in reactions with trimethylsilyl derivatives Me 3 SiY is formation of a compound with a stronger O6Si coordination bond [3].It was previously established that the N,N-bis-(acetyl)aminomethyl ligand, like amidomethyl [4] and lactamomethyl [5,6], exhibits chelating ability. Proceeding with this research, we prepared N-chlorodimethylsilyl derivatives of 5-and 6-membered cyclic imides of dicarboxylic acids and studied the effect of the size of the imide ring on the strength of O6Si coordination. The structures of the products in different aggregative states were established by NMR spectroscopy and X-ray diffraction analysis, as well as by quantum-chemical calculations. N-(Chlorodimethylsilylmethyl)amides,-lactams, and imides are most commonly prepared by reactions of their N-trimethylsilyl derivatives with chloro(chloromethyl)dimethylsilane [4,6,7]. Despite the fact that this synthesis involves many stages (initial formation of transsilylation product, followed by O-silylmethylation, and, finally, N-silylmethylation), it usually proceeds very smoothly with practically quantitative yields of N-silylmethyl derivatives [1]. We made use of this method for preparing cyclic N-(chlorodimeth...

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Crystal structure of organosilicon compounds. XLVII. 1-(chlorodimethylsilylmethyl)-2-piperidone

Cited by 10 publications

References 9 publications

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Hexacoordination via Sulfur Donor Action in Nitrogen and Chlorine Bonded Bicyclic Tetraoxyphosphoranes¹

Synthesis, structure, and spatial arrangement of Si-substituted N-(dimethylsilylmethyl)imides

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Crystal structure of organosilicon compounds. XLVII. 1-(chlorodimethylsilylmethyl)-2-piperidone

Cited by 10 publications

References 9 publications

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Structures and stereochemical non-rigidity of Si-substituted N-(dimethylsilylmethyl)- and N-(methylphenylsilylmethyl)amides and -lactams

Hexacoordination via Sulfur Donor Action in Nitrogen and Chlorine Bonded Bicyclic Tetraoxyphosphoranes1

Synthesis, structure, and spatial arrangement of Si-substituted N-(dimethylsilylmethyl)imides

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Hexacoordination via Sulfur Donor Action in Nitrogen and Chlorine Bonded Bicyclic Tetraoxyphosphoranes¹