Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone

Sergey Yu Bylikin; Aleksandr G. Shipov; Vadim V. Negrebetsky; Yuri I. Baukov; Yuri E. Ovchinnikov; Sergei A. Pogozhikh; Sergei V. Pestunovich; Lyudmila I. Belousova; Elena F. Belogolova; Valery F. Sidorkin; Mikhail G. Voronkov; Vadim A. Pestunovich; Inna Kalikhman; Daniel Kost

doi:10.1016/j.jorganchem.2005.05.052

Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone

Sergey Yu Bylikin, Aleksandr G. Shipov, Vadim V. Negrebetsky, Yuri I. Baukov, Yuri E. Ovchinnikov, Sergei A. Pogozhikh, Sergei V. Pestunovich, Lyudmila I. Belousova, Elena F. Belogolova, Valery F. Sidorkin, Mikhail G. Voronkov, Vadim A. Pestunovich, Inna Kalikhman, Daniel Kost

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

A general scheme of reactions between chloro(chloromethyl)dimethylstannane and N-trimethylsilylamides and -lactams was established by NMR and IR techniques. The reactions proceed via transmetallation followed by transformation of the N-stannylated intermediate (1) into (N-Sn)-coordinated O-stannylmethyl (2) and (O-Sn)-coordinated N-stannylmethyl (3) derivatives. In the cases of 2-piperidone and 2-hexahydroazepinone these products were isolated as individual compounds (2b,c and 3b,c). X-ray diffraction study of 1-(chlorodimethylstannylmethyl)-2-piperidone (3b) confirmed (3 + 2) -coordination state of the tin atom and axial positions of oxygen and halogen atoms. The experimental and quantum-chemically calculated structural parameters are discussed in comparison with those of related trigonal bipyramidal (TBP) silicon, germanium and tin derivatives. Calculation at the MP2/LanL2DZ/D95 level reveals that the stability of the (O-M)chelates increases in the following order: (O-Si) < (O-Ge) < (O-Sn).

Original language	English
Pages (from-to)	779-786
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	691
Issue number	4
DOIs	https://doi.org/10.1016/j.jorganchem.2005.05.052
State	Published - 1 Feb 2006

Keywords

H, C, N and Sn NMR spectra
Intramolecular coordination
MP2/LanL2DZ/D95 calculations
Synthesis
Tin
X-ray study

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jorganchem.2005.05.052

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Bylikin, S. Y., Shipov, A. G., Negrebetsky, V. V., Baukov, Y. I., Ovchinnikov, Y. E., Pogozhikh, S. A., Pestunovich, S. V., Belousova, L. I., Belogolova, E. F., Sidorkin, V. F., Voronkov, M. G., Pestunovich, V. A., Kalikhman, I., & Kost, D. (2006). Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone. Journal of Organometallic Chemistry, 691(4), 779-786. https://doi.org/10.1016/j.jorganchem.2005.05.052

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title = "Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone",

abstract = "A general scheme of reactions between chloro(chloromethyl)dimethylstannane and N-trimethylsilylamides and -lactams was established by NMR and IR techniques. The reactions proceed via transmetallation followed by transformation of the N-stannylated intermediate (1) into (N-Sn)-coordinated O-stannylmethyl (2) and (O-Sn)-coordinated N-stannylmethyl (3) derivatives. In the cases of 2-piperidone and 2-hexahydroazepinone these products were isolated as individual compounds (2b,c and 3b,c). X-ray diffraction study of 1-(chlorodimethylstannylmethyl)-2-piperidone (3b) confirmed (3 + 2) -coordination state of the tin atom and axial positions of oxygen and halogen atoms. The experimental and quantum-chemically calculated structural parameters are discussed in comparison with those of related trigonal bipyramidal (TBP) silicon, germanium and tin derivatives. Calculation at the MP2/LanL2DZ/D95 level reveals that the stability of the (O-M)chelates increases in the following order: (O-Si) < (O-Ge) < (O-Sn).",

keywords = "H, C, N and Sn NMR spectra, Intramolecular coordination, MP2/LanL2DZ/D95 calculations, Synthesis, Tin, X-ray study",

author = "Bylikin, \{Sergey Yu\} and Shipov, \{Aleksandr G.\} and Negrebetsky, \{Vadim V.\} and Baukov, \{Yuri I.\} and Ovchinnikov, \{Yuri E.\} and Pogozhikh, \{Sergei A.\} and Pestunovich, \{Sergei V.\} and Belousova, \{Lyudmila I.\} and Belogolova, \{Elena F.\} and Sidorkin, \{Valery F.\} and Voronkov, \{Mikhail G.\} and Pestunovich, \{Vadim A.\} and Inna Kalikhman and Daniel Kost",

year = "2006",

month = feb,

day = "1",

doi = "10.1016/j.jorganchem.2005.05.052",

language = "English",

volume = "691",

pages = "779--786",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "4",

}

Bylikin, SY, Shipov, AG, Negrebetsky, VV, Baukov, YI, Ovchinnikov, YE, Pogozhikh, SA, Pestunovich, SV, Belousova, LI, Belogolova, EF, Sidorkin, VF, Voronkov, MG, Pestunovich, VA, Kalikhman, I & Kost, D 2006, 'Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone', Journal of Organometallic Chemistry, vol. 691, no. 4, pp. 779-786. https://doi.org/10.1016/j.jorganchem.2005.05.052

Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone. / Bylikin, Sergey Yu; Shipov, Aleksandr G.; Negrebetsky, Vadim V. et al.
In: Journal of Organometallic Chemistry, Vol. 691, No. 4, 01.02.2006, p. 779-786.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane

T2 - Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone

AU - Bylikin, Sergey Yu

AU - Shipov, Aleksandr G.

AU - Negrebetsky, Vadim V.

AU - Baukov, Yuri I.

AU - Ovchinnikov, Yuri E.

AU - Pogozhikh, Sergei A.

AU - Pestunovich, Sergei V.

AU - Belousova, Lyudmila I.

AU - Belogolova, Elena F.

AU - Sidorkin, Valery F.

AU - Voronkov, Mikhail G.

AU - Pestunovich, Vadim A.

AU - Kalikhman, Inna

AU - Kost, Daniel

PY - 2006/2/1

Y1 - 2006/2/1

N2 - A general scheme of reactions between chloro(chloromethyl)dimethylstannane and N-trimethylsilylamides and -lactams was established by NMR and IR techniques. The reactions proceed via transmetallation followed by transformation of the N-stannylated intermediate (1) into (N-Sn)-coordinated O-stannylmethyl (2) and (O-Sn)-coordinated N-stannylmethyl (3) derivatives. In the cases of 2-piperidone and 2-hexahydroazepinone these products were isolated as individual compounds (2b,c and 3b,c). X-ray diffraction study of 1-(chlorodimethylstannylmethyl)-2-piperidone (3b) confirmed (3 + 2) -coordination state of the tin atom and axial positions of oxygen and halogen atoms. The experimental and quantum-chemically calculated structural parameters are discussed in comparison with those of related trigonal bipyramidal (TBP) silicon, germanium and tin derivatives. Calculation at the MP2/LanL2DZ/D95 level reveals that the stability of the (O-M)chelates increases in the following order: (O-Si) < (O-Ge) < (O-Sn).

AB - A general scheme of reactions between chloro(chloromethyl)dimethylstannane and N-trimethylsilylamides and -lactams was established by NMR and IR techniques. The reactions proceed via transmetallation followed by transformation of the N-stannylated intermediate (1) into (N-Sn)-coordinated O-stannylmethyl (2) and (O-Sn)-coordinated N-stannylmethyl (3) derivatives. In the cases of 2-piperidone and 2-hexahydroazepinone these products were isolated as individual compounds (2b,c and 3b,c). X-ray diffraction study of 1-(chlorodimethylstannylmethyl)-2-piperidone (3b) confirmed (3 + 2) -coordination state of the tin atom and axial positions of oxygen and halogen atoms. The experimental and quantum-chemically calculated structural parameters are discussed in comparison with those of related trigonal bipyramidal (TBP) silicon, germanium and tin derivatives. Calculation at the MP2/LanL2DZ/D95 level reveals that the stability of the (O-M)chelates increases in the following order: (O-Si) < (O-Ge) < (O-Sn).

KW - H, C, N and Sn NMR spectra

KW - Intramolecular coordination

KW - MP2/LanL2DZ/D95 calculations

KW - Synthesis

KW - Tin

KW - X-ray study

UR - http://www.scopus.com/inward/record.url?scp=30844470855&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2005.05.052

DO - 10.1016/j.jorganchem.2005.05.052

M3 - Article

AN - SCOPUS:30844470855

SN - 0022-328X

VL - 691

SP - 779

EP - 786

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 4

ER -

Bylikin SY, Shipov AG, Negrebetsky VV, Baukov YI, Ovchinnikov YE, Pogozhikh SA et al. Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone. Journal of Organometallic Chemistry. 2006 Feb 1;691(4):779-786. doi: 10.1016/j.jorganchem.2005.05.052

Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone

Abstract

Keywords

ASJC Scopus subject areas

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