How hydrogen-bonded MnO4- can influence oxidation of olefins in both gas phase and solution?
Article first published online: 23 JUL 2012
Copyright © 2012 John Wiley & Sons, Ltd.
Journal of Physical Organic Chemistry
Volume 25, Issue 12, pages 1198–1209, December 2012
How to Cite
2012), How hydrogen-bonded MnO4- can influence oxidation of olefins in both gas phase and solution?, Journal of Physical Organic Chemistry. DOI: 10.1002/poc.2992, , , (
- Issue published online: 7 JAN 2013
- Article first published online: 23 JUL 2012
- Manuscript Accepted: 12 JUN 2012
- Manuscript Revised: 21 MAY 2012
- Manuscript Received: 11 JAN 2012
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- hydrogen bonding;
- ethylene glycol;
- oxidation reaction
The reaction pathway (including the transition state) of ethylene addition to permanganate (MnO4-) in the presence of ethylene glycol (EG) has been qualitatively and quantitatively studied by means of B3LYP/6-311++G** theoretical analysis. Interestingly, by cluster formation of the EG with permanganate, oxidation reaction becomes thermodynamically and kinetically more favorable. The influences of electron-withdrawing as well as electron-donating substituents were also explored.
Results of the quantum theory of atoms in molecules and natural bond orbital analyses revealed that [3 + 2] addition reaction of alkenes in the presence of EG as hydrogen bonding donor to MnO4- becomes more exothermic. Natural resonance theory (NRT) is used to calculate natural bond order and bond polarity. The NRT result indicates that the polarity of Mn–O bond is affected by EG coordinated to MnO4-. Moreover, the conceptual DFT descriptors such as chemical potential (μ), hardness (η) and electrophilicity index (ω) show that hydrogen bonding to permanganate can affect the addition of MnO4- to double bond in a satisfactory way. We also carried out geometrical optimizations with the polarizable continuum model to account for the solvent effect, and the results were compared with those in the gas phase. Copyright © 2012 John Wiley & Sons, Ltd.
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