@article{ShainyanKirpichenkoKleinpeteretal.2013,
  author    = {Shainyan, Bagrat A. and Kirpichenko, Svetlana V. and Kleinpeter, Erich and Shlykov, Sergey A. and Osadchiy, Dmitriy Yu and Chipanina, Nina N. and Oznobikhina, Larisa P.},
  title     = {1,3-Dimethy1-3-silapiperidine - synthesis, molecular structure, and conformational analysis by gas-phase electron diffraction, low temperature NMR, IR and Raman Spectroscopy, and quantum chemical calculations},
  series = {The journal of organic chemistry},
  volume    = {78},
  journal   = {The journal of organic chemistry},
  number    = {8},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0022-3263},
  doi       = {10.1021/jo400289g},
  pages     = {3939 -- 3947},
  year      = {2013},
  abstract  = {The first Si-H-containing azasilaheterocycle, 1,3-dimethyl-3-silapiperidine 1, was synthesized, and its molecular structure and conformational properties were studied by gas-phase electron diffraction (GED), low temperature NMR, IR and Raman spectroscopy and quantum chemical calculations. The compound exists as a mixture of two conformers possessing the chair conformation with the equatorial NMe group and differing by axial or equatorial position of the SiMe group. In the gas phase, the SiMeax conformer predominates (GED: ax/eq = 65(7):35(7)\%,Delta G = 0.36(18) kcal/mol; IR: ax/eq = 62(5):38(5)\%,Delta G = 0.16(7) kcal/mol). In solution, at 143 k the SiMeeq conformer predominates' in the frozen equilibrium (NMR: ax/eq = 31.5(1.5):68.5(1.5)\%, Delta G = -0.22(2) kcal/mol). Thermodynamic parameters of the ring inversion are determined (Delta G(double dagger) = 8.9-9.0 kcal/mol, Delta H-double dagger = 9.6 kcal/mol, Delta S-double dagger = 2.1 eu). High-level quantum chemical calculations :(MP2, G2, CCSD(T)) nicely reproduce the experimental geometry and the predominance of the axial conformer in the gas phase.},
  language  = {en}
}
@article{LazarevaShainyanSchildeetal.2012,
  author    = {Lazareva, Nataliya F. and Shainyan, Bagrat A. and Schilde, Uwe and Chipanina, Nina N. and Oznobikhina, Larisa P. and Albanov, Alexander I. and Kleinpeter, Erich},
  title     = {Synthesis, molecular structure, conformational analysis, and chemical properties of silicon-containing derivatives of quinolizidine},
  series = {The journal of organic chemistry},
  volume    = {77},
  journal   = {The journal of organic chemistry},
  number    = {5},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0022-3263},
  doi       = {10.1021/jo202658n},
  pages     = {2382 -- 2388},
  year      = {2012},
  abstract  = {A silicon analog of quinolizidine 3,3,7,7-tetramethylhexahydro-1H-[1,4,2]oxazasilino[4,5-d][1,4,2]oxazasilin-9a-yl)methanol 3 was synthesized. X-ray diffraction analysis confirmed the trans configuration and low temperature NMR spectroscopy both the flexibility (barrier of interconversion 5.8 kcal mol(-1)) and the conformational equilibrium (chair-chair and chair-twist conformers) of the compound. The relative stability of the different isomers/conformers of 3 was calculated also at the MP2/6-311G(d,p) level of theory. Intra- and intermolecular hydrogen bonding in 3 and the appropriate equilibrium between free and self-associated molecules was studied in solvents of different polarity. Both the N-methyl quaternary ammonium salt and the O-trimethylsilyl derivative of 3 could be obtained and their structure determined.},
  language  = {en}
}
@article{ShainyanKirpichenkoChipaninaetal.2015,
  author    = {Shainyan, Bagrat A. and Kirpichenko, Svetlana V. and Chipanina, Nina N. and Oznobikhina, Larisa P. and Kleinpeter, Erich and Shlykov, Sergey A. and Osadchiy, Dmitriy Yu.},
  title     = {Synthesis and Conformational Analysis of 3-Methyl-3-silatetrahydropyran by GED, FTIR, NMR, and Theoretical Calculations: Comparative Analysis of 1-Hetero-3-methyl-3-silacyclohexanes},
  series = {The journal of organic chemistry},
  volume    = {80},
  journal   = {The journal of organic chemistry},
  number    = {24},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0022-3263},
  doi       = {10.1021/acs.joc.5b02355},
  pages     = {12492 -- 12500},
  year      = {2015},
  abstract  = {3-Methyl-3-silatetrahydropyran 1 was synthesized and its molecular structure and conformational behavior was studied by gas-phase electron diffraction (GED), FTIR, low temperature H-1 and C-13 NMR spectroscopy, and by theoretical calculations (DFT, MP2). Two conformers; 1-ax and 1-eq; were located on the potential energy Surface. In the gas phase; a slight predominance of the axial conformer was determined, with the ratio 1-ax:1-eq = 54(9):46(9) (from GED) or 53:47 or 61;39 (from IR). In solution, LT NMR spectroscopy at 103 K gives the ratio 1-ax:1-eq = 35:65 (-Delta G(103)degrees = 0.13 kcal/mol). Simulation of solvent effects using the PCM continuum model or by calculation of the corresponding solvent-solute complexes allowed us to rationalize the experimentally observed opposite conformational predominance of the conformers of 3-methyl-3-silatettahydropyran in the gas phase and in solution. Comparative analysis of the effect of heteroatom in 1-hetero-3-methyl-3-silacyclohexanes on the structure, stereoelectronic interactions, and relative energies of the conformers is done.},
  language  = {en}
}