Structure-correlation principles connecting ground state properties and reaction barrier heights for the Cope rearrangement of semibullvalenes.
A direct relationship exists between the properties of substituted semibullvalenes and their Cope rearrangement activation barrier. This unique correlation not only enables the determination of kinetic data from ground state information, but also provides a rationalization for the extent to which ground state properties are altered with respect to their "normal" values (i.e., that of their localized Lewis structure). Examination of electron density distribution, geometrical parameters, and J-coupling constant differences between canonical and Lewis structures deliver quantitative evidence for the structure-correlation principle.
Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.
Daniel F
DF
Jana
Matthew D
MD
Wodrich
Clémence
C
Corminboeuf
D003516:Cycloparaffins / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory
D003516:Cycloparaffins