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How hydrogen-bonded MnO4- can influence oxidation of olefins in both gas phase and solution?
Javan, M. J ; Sharif University of Technology | 2012
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- Type of Document: Article
- DOI: 10.1002/poc.2992
- Publisher: 2012
- Abstract:
- 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 MnO 4- 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
- Keywords:
- Hydrogen bonding ; Oxidation reaction ; B3LYP/6-311++G ; Cluster formations ; Descriptors ; Double bonds ; Electron-donating substituents ; Electronwithdrawing ; Electrophilicity index ; Gasphase ; Geometrical optimization ; Natural bond orbital analysis ; Natural bond orders ; Natural resonance ; Oxidation reactions ; permanganate ; Polarizable continuum model ; Quantum Theory of Atoms in Molecules ; Reaction pathways ; Solvent effects ; Transition state ; Addition reactions ; Continuum mechanics ; Ethylene ; Ethylene glycol ; Gases ; Hydrocarbons ; Hydrogen bonds ; Manganese ; Quantum theory ; Manganese oxide
- Source: Journal of Physical Organic Chemistry ; Volume 25, Issue 12 , 2012 , Pages 1198-1209 ; 08943230 (ISSN)
- URL: http://onlinelibrary.wiley.com/doi/10.1002/poc.2992/abstract