TY  - JOUR
A1  - Shainyan, Bagrat A.
A1  - Kirpichenko, Svetlana V.
A1  - Chipanina, Nina N.
A1  - Oznobikhina, Larisa P.
A1  - Kleinpeter, Erich
A1  - Shlykov, Sergey A.
A1  - Osadchiy, Dmitriy Yu.
T1  - 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
T2  - The journal of organic chemistry
N2  - 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.
Y1  - 2015
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/38368
SN  - 0022-3263
VL  - 80
IS  - 24
SP  - 12492
EP  - 12500
PB  - American Chemical Society
CY  - Washington
ER  -