New PDF release: acetylene chermistry

By F. Diederich, P. J. Stang, R. R. Tykwinski

ISBN-10: 3527305181

ISBN-13: 9783527305186

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ISBN-13: 9783527306718

ISBN-10: 3527307133

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ISBN-10: 3527307141

ISBN-13: 9783527307142

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8) have been calculated at the B3LYP/6-31+G* level. The molecular flexibility of these compounds is different in the gas phase and in aqueous solution, as evidenced by classical molecular dynamics (MM3 force-field) [80]. Even at low temperature, free ring twisting dominates in the gas phase, becoming almost periodic after a few picoseconds of equilibration, while random conformations are predicted in solution. This random twisting is expected to affect the fluorescence properties of these compounds significantly.

6-31G* [126], or B3PW91/6-31G** [127] levels of theory. 3). Structural criterion. Despite a planar equilibrium structure, the bond lengths and angles are very close to those calculated in 1,4-pentadiynes, ruling out any structural homoaromaticity. Energetic criterion. The energetic homoaromaticity of a cyclic molecule is measured by its stability with respect to acyclic reference molecules. 2 kcal mol–1) [125]. 8 kcal mol–1 [126]. [5]Pericyclyne is therefore not energetically homoaromatic. The stability of [5]pericyclynes with respect to cyclic isomers has also been considered.

10 Expanded [4] pericyclynic rings. 6-31G* [126], or B3PW91/6-31G** [127] levels of theory. 3). Structural criterion. Despite a planar equilibrium structure, the bond lengths and angles are very close to those calculated in 1,4-pentadiynes, ruling out any structural homoaromaticity. Energetic criterion. The energetic homoaromaticity of a cyclic molecule is measured by its stability with respect to acyclic reference molecules. 2 kcal mol–1) [125]. 8 kcal mol–1 [126]. [5]Pericyclyne is therefore not energetically homoaromatic.

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acetylene chermistry by F. Diederich, P. J. Stang, R. R. Tykwinski


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