Conformational properties of 1-cyano-1-silacyclohexane, C5H10SiHCN: Gas electron diffraction, low-temperature NMR and quantum chemical calculations☆

Abstract The conformational preference of the cyano group of the 1-cyano-1-silacyclohexane was studied experimentally by means of gas electron diffraction (GED) and dynamic nuclear magnetic resonance (DNMR) as well as by quantum chemical (QC) calculations applying high-level coupled cluster methods as well as DFT methods. According to the GED experiment, the compound exists in the gas-phase as a mixture of two conformers possessing the chair conformation of the six-membered ring and C s symmetry while differing in the axial or equatorial position of the substituent (axial = 84(12) mol %/equatorial = 16(12) mol %) at T  = 279(3) K, corresponding to an A value ( G ax – G eq ) of −1.0(4) kcal mol −1 . Gas-phase CCSD(T) calculations predict an A value of −0.72 kcal mol −1 at 279 K. In contrast, the low-temperature 13 C NMR experiments resulted in an axial/equatorial ratio of 35/65 mol % at 120 K corresponding to an A value of 0.14 kcal mol −1 . An average value for Δ G # e→a  = 5.6 ± 0.1 kcal mol −1 was obtained for the temperature range 110–145 K. The dramatically different conformational behaviour in the gas-phase (GED) compared to the liquid phase (DNMR) suggests a strong solvation effect. According to natural bond orbital analysis the axial conformer of the title compound is an example of stabilization of a form, which is not favored by electrostatic effects and is favored predominantly by steric and conjugation effects.