The Alpha-Effect. A Theoretical Study Incorporating Solvent Effects
نویسندگان
چکیده
Several recent studies have shown that OOHhas no greater reactivity than oHin the gas phase. This is in striking contrast to the solution phase observation that OOHhas 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 OOHover OHin solution.
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