Structure and conformational behavior of N-phenylpiperidine studied by gas-phase electron diffraction and quantum chemical calculations.

Molecular structure and conformational behavior of N -phenylpiperidine ( NPhP ) were investigated by synchronous gas-phase electron diffraction/mass spectrometry (GED/MS) and quantum chemistry. Due to influence of steric repulsion and hyperconjugation, NPhP may exist in two conformers, equatorial and axial chair forms. Both experiment and theoretical calculations suggest a C 1 symmetry of the conformers, with the plane perpendicular to the phenyl group turned by ca. 30–40° (equatorial) and 0–20° (axial) about the plane perpendicular to the piperidine ring symmetry plane. According to the QC calculations, NPhP may exist as two conformers, equatorial and axial, with a ratio of Eq:Ax = 92:8 (B3LYP), 87:13 (B3LYP-GD3), 84:16 (M06-2X), 83:17 (MP2/6-311G**) and 76:24% (MP2/cc-pVTZ). Except for the latter, these values are in good agreement with the experimental GED data of 90(10):10(10)%. A comparative analysis of similar compounds, phenylcyclohexane and 1-phenylheterocyclohexanes, was performed. Conformational properties depend on the C Ph X bond distance and hyperconjugation between the phenyl ring and the lone pair on the heteroatom. The contribution of the axial form of 1-phenylcyclohexane derivatives increases in the series of the heteroatom X in the cyclohexane ring: C → N → Si → P. [ABSTRACT FROM AUTHOR]