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

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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 languageEnglish
Pages (from-to)779-786
Number of pages8
JournalJournal of Organometallic Chemistry
Volume691
Issue number4
DOIs
StatePublished - 1 Feb 2006

Keywords

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

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