|
KMID : 1059519840280040217
|
|
Journal of the Korean Chemical Society
1984 Volume.28 No. 4 p.217 ~ p.230
|
|
|
Determination of Reactivity by MO Theory (XXXIV). MINDO/3 Theoretical Studies on Sigmatropic Hydrogen Rearrangements (1) : Systems with Central Carbon Atom
|
|
Cho Jeoung-Ki
Lee Ik-Choon
Oh Hyuck-Keun
Cho In-Ho
|
|
|
Abstract
|
|
|
|
The MINDO/3 method was used in determination of transition states and activation barriers for various 1,2-, 1,3- and 1,5-sigmatropic hydrogen rearrangements involving systems with central carbon atom. It was found that, besides the consideration of orbital symmetry, steric effect, aromaticity, and orbital interactions were found to dictate the stability of the transition state. For systems with hetero atoms, lone pair orbitals tend to ease orbital distortion required at the transition state by participating in hydrogen transfer process and were found to lower the activation barrier accordingly. Comparison of the relative barrier heights with those obtained by using more sophisticated ab initio MO calculations showed that the MINDO/3 results give qualitatively the same tendency of the relative order of the activation barriers.
|
|
|
KEYWORD
|
|
|
|
|
|
FullTexts / Linksout information
|
|
|
|
|
|
Listed journal information
|
|
|