Kratko priopćenje

The Alpha-Effect. A Theoretical Study Incorporating Solvent Effects

Gilles Klopman ; Department of Chemistry, Case Western Reserve University, Cleveland, OH 44106
Manton R. Frierson ; Department of Chemistry, Case Western Reserve University, Cleveland, OH 44106

Sažetak

Several recent studies have shown that OOH- has no greater
reactivity than oH- in the gas phase. This is in striking contrast
to the solution phase observation that OOH- has an enhanced
nucleophilicity over oH- (the "alpha-effect"). The gas-phase
results were thought to put into jeopardy the FMO orbital-splitting
explanation of the alpha-effect, since, it was reasoned, such an
effect should be independent of solvent. However, the calculations
reported here, based on MIND0/3 and solvaton theory (to take
account of the effects of solvent), show that the extrapolation of
the gas-phase results to solution is invalid and that orbital-
splitting does play an important role in the enhanced nucleophilicity
of OOH- over OH- in solution.

Ključne riječi

Hrčak ID:

194032

URI

https://hrcak.srce.hr/194032

Datum izdavanja:

21.5.1985.

Posjeta: 1.193 *