TY - JOUR
T1 - n,π-Interactions in Polycyclic Unsaturated Ketones
T2 - Photoelectron Spectroscopic Study
AU - Kovač, Branka
AU - Novak, Igor
AU - Mlinarić-Majerski, Kata
AU - Vinković, Marijana
AU - Kaselj, Mira
PY - 1994/6/1
Y1 - 1994/6/1
N2 - He I photoelectron spectra (PE) of several β,γ-unsaturated polycyclic ketones, their parent ketones, and alkenes have been measured. The assignment of spectra is based on semiempirical MO calculations (PM3 method) and empirical arguments. Endo-derivatives showed larger HOMO/SHOMO band separation than exo-cyclic unsaturated ketones. The results of MO calculations are in good agreement with this general trend. Strikingly different photochemical transformations and π* ⟸ n electronic transition intensities, exhibited by the two groups of compounds, can be rationalized within the framework of oxygen lone pair ↔ π bond interactions.
AB - He I photoelectron spectra (PE) of several β,γ-unsaturated polycyclic ketones, their parent ketones, and alkenes have been measured. The assignment of spectra is based on semiempirical MO calculations (PM3 method) and empirical arguments. Endo-derivatives showed larger HOMO/SHOMO band separation than exo-cyclic unsaturated ketones. The results of MO calculations are in good agreement with this general trend. Strikingly different photochemical transformations and π* ⟸ n electronic transition intensities, exhibited by the two groups of compounds, can be rationalized within the framework of oxygen lone pair ↔ π bond interactions.
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U2 - 10.1021/jo00090a021
DO - 10.1021/jo00090a021
M3 - Article
AN - SCOPUS:0012808386
SN - 0022-3263
VL - 59
SP - 3033
EP - 3036
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 11
ER -