• Bulletin of the Korean Chemical Society
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• v.27 no.7
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• pp.1009-1014
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• 2006

Density functional theory calculations are applied to investigate the intramolecular proton transfer in the tautomers of thymine radical cation and its hydrated complexes with one water molecule. The optimized structures and energies for 6 tautomers and 6 transition states of thymine radical cation are calculated at the B3LYP/6-311++G(d,p) level. It is predicted that the order of relative stability for the keto and enol tautomers of thymine radical cation is the same with that of the neutral thymine tautomers, though the enol tautomers are more stabilized with respect to the di-keto form in the radical cation than in the neutral state. A new channel of proton transfer from >C5-$CH_{3}$ of thymine is found to open and have the lowest energy barrier of other proton transfer processes in thymine radical cation. The roles of hydration are also investigated with thymine-water 1 : 1 complex ions. The presence of water significantly lowers the barrier of the proton transfer, which clearly shows the assisting role of hydration even with one water molecule

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.729-730
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• 2009

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.103-106
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• 2002

A new reaction mechanism is proposed for the reaction of thianthrene cation radical perchlorate $(Th^{+{\cdot}}CIO_4^-}$ and tert-butyl peroxide in acetonitrile at room temperature on the basis of experimental and theoretical results. Rapid C-O bond rupture instead of O-O bond cleavage was observed by a good peroxy radical trapping agent, thianthrene cation radical. Products were N-tert-butyl acetamide, thianthrene 5-oxide (ThO), thianthrene 5,5-dioxide $(SSO_2)$, and thianthrene (Th). Thianthrene 5,10-dioxide (SOSO) was not obtained. A comparative computational study of the cation radical of tert-butyl peroxide is made by using B3LYP and CBS-4. The computational results are helpful to explain the reaction mechanism.

• Bulletin of the Korean Chemical Society
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• v.1 no.3
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• pp.98-101
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• 1980

For the first time we have synthesized thiabenzene radical by the reaction of thiopyrylium cation with alkali metals. As might be expected for a free radical, ESR-spectrum of 2,4,6-triphenylthiabenzene radical shows the single signal with g-value of 2.0045. The proton signal of 2,4,6-triphenylthiabenzene radical in nmr spectrum shifts to the higher field than that of 2,4,6-triphenylthiopyrylium cation by ca. 0.5 ppm. From the UV-spectrum of thiabenzene radical the presence of 6${\pi}$ non-benzenoid aromatic system was observed as in the case of thiopyrylium cation. The reactivity of alkali metals with thiopyrylium cation increases in the order of decreasing ionization energy, Li

• Bulletin of the Korean Chemical Society
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• v.26 no.9
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• pp.1335-1338
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• 2005

Thianthrene cation radical perchlorate ($Th^{+{{\cdot}}}{ClO_4}^-$) reacted readily with two isomeric thiols, benzylthiol (1) and 4-methylbenzenethiol (7) in an acetonitrile solution at room temperature. From the reaction of 1, the major products, N-benzylacetamide (4) and benzyl sulfide (5), are characteristic of benzyl carbocations while the minor one, benzyl disulfide (6) implies free radical component of the reaction. It is unprecedented that the formation of a benzyl carbocation was caused by the extrusion of sulfur atoms from benzyl sulfur cations (3). In contrast, from the reaction of 7, only p-tolyl disulfide (10) was obtained from both sulfur radicals and cations. In the reaction of 7 the thio-extrusion was not observed from the p-tolyl sulfur cation (9). A thianthrene cation radical ($Th^{+{{\cdot}}}$) was reduced quantitatively to thianthrene (Th) in both reactions.

• Journal of the Korean Magnetic Resonance Society
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• v.6 no.2
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• pp.103-112
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• 2002

The photoproduced cation radical of N-methylphenothiazine $(PC_1)$ doped into phenyltriehtoxysilane (PhiTEOS), vinyltriethoxysilane (VTEOS) and methyltriethoxysilane (METOS) was studied with electron spin resonance (ESR) and electron nuclear double resonance (ENDOR). The photoinduced charge separation efficiency was determined by integration of ESR spectra which correspond to the amount of photoproduced cation radical in the matrices. This was correlatively studied with the polarity and pore size of the gel matrices. The relative polarity of the matrices was determined by measuring ${\lambda}_{max}$ values of $PC_1$ in the different matrices. The relative pore size among the matrices was determined by measuring relative proton matrix ENDOR line widths of the photoproduced cation of $PC_1$. The decay kinetic constants of the cation radical of $PC_1$ in the different matrices with relatively studied with fitting the biexponential decay curves after exposure at the ambient condition. This is correlatively interpreted with the polarity and pore size of the matrices.

• Journal of Integrative Natural Science
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• v.5 no.2
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• pp.127-130
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• 2012

Polymerization of vinyl monomers is promoted by thianthrene cation radical as a part of our research concerning the reactions of various agents with readily isolable, yet highly reactive species and elucidate the biological activity. Thianthrene cation radical initiated the homopolymerization and copolymerization of styrene and ethyl vinyl ether. The polymerization yields decreased as the concentration of phenylacetylene or diphenylethylene increased. Such polymereization by cationic thianthrene radical could provide some clues for the reaction in living animals. Comments on possible polymerization mechanisms were suggested.

• Applied Chemistry for Engineering
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• v.5 no.3
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• pp.438-442
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• 1994

A very useful cation radical, triphenylaminium hexachloroantimonate, was quantitatively incorporated into insoluble polymer framework. The polymer cation radical was found to be effective as a catalyst in the Diels-Alder type dimerization and then shown to be reusable through several cycles of use.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3249-3252
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• 2013

We have explored the potential energy surface for the isomerization of the aniline (AN) radical cation to the 2-, 3-, and 4-methylpyridine (picoline, MP) radical cations using G3 model calculations. The isomerization may occur through the 1H-azepine (7-aza-cycloheptatriene) radical cation. A quantitative kinetic analysis has been performed using the Rice-Ramsperger-Kassel-Marcus theory, based on the potential energy surface. The result shows that isomerization between $AN^{+\bullet}$ and each $MP^{+\bullet}$ hardly occurs before their dissociations.

• Bulletin of the Korean Chemical Society
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• v.5 no.6
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• pp.211-215
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• 1984

Reaction of thianthrene cation radical perchlorate (1) with tert-butyl peroxide (TBP) in acetonitrile gave thianthrene (2), thianthrene 5-oxide (3), cis-thianthrene-5,10-dioxide (4), 5-acetonylthianthrenium perchlorate (9), along with small amount of thianthrene-5,5-dioxide (7) in some cases. Isolation of N-tert-butylacetamide indicated the formation of tert-butyl cation from TBP. The formation mechanisms of these products were proposed.