Reaction of N-trimethylsilyl derivatives of amides and lactams with chloro(chloromethyl)dimethylstannane: Crystal and molecular structure of 1-(chlorodimethylstannylmethyl)-2-piperidone
| Autor: | L. I. Belousova, Vadim V. Negrebetsky, Valery F. Sidorkin, Daniel Kost, Sergei V. Pestunovich, Yuri E. Ovchinnikov, Sergey Yu. Bylikin, Sergei A. Pogozhikh, Aleksandr G. Shipov, Yuri I. Baukov, Voronkov Mikhail G, Elena F. Belogolova, Inna Kalikhman, V. A. Pestunovich |
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| Rok vydání: | 2006 |
| Předmět: |
Trimethylsilyl
Organic Chemistry chemistry.chemical_element Germanium Biochemistry Inorganic Chemistry chemistry.chemical_compound Crystallography Trigonal bipyramidal molecular geometry Transmetalation chemistry Halogen X-ray crystallography Materials Chemistry Molecule Physical and Theoretical Chemistry Tin |
| Zdroj: | Journal of Organometallic Chemistry. 691:779-786 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2005.05.052 |
| Popis: | 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) |
| Databáze: | OpenAIRE |
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