• Bulletin of the Korean Chemical Society
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• 제29권10호
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• pp.1898-1904
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• 2008

Study of computational model of the concerted Diels-Alder reaction between 9,10-dimethyl anthracene (as donor) and tetracyanoethylene (as acceptor) in absence and in presence of aromatic solvents (benzene, mesitylene and hexamethylbenzene, as donors) using an AM1 semi-empirical method. AM1 method used to study the neutral charge transfer complex models that could be expected between donor and acceptor during the course of the concerted Diels-Alder reaction. Calculated enthalpies of reaction of the charge transfer complexes models showed physical and chemical meaning for explain the effect of aromatic solvents on the kinetic process of concerted Diels-Alder reaction that contains tetracyanoethylene.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1181-1185
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• 1999

The reaction of FeC5H5+ ion with ferrocene molecule is investigated using FT-ICR mass spectrometry. FeC5H5+ ions are generated by dissociative ionization of ferrocenes using an electron beam. The reaction gives rise to the formation of the adduct ion, Fe2(C5H5)3+, in competition with charge transfer reaction leading to the formation of ferrocene molecular ion, Fe(C5H5)2+·. The branching ratio of the adduct ion increases as the internal energy of the reactant ion decreases and correspondingly the branching ratio for the charge transfer reaction product decreases. The observed rate of the addition reaction channel is slower than that of the charge transfer reaction. The observation of the stable adduct ions in the low-pressure ICR cell is attributed to the radiative cooling of the activated ion-molecule complex. The mechanism of the reaction is presented to account for the observed experimental results.

• Bulletin of the Korean Chemical Society
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• 제6권3호
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• pp.145-148
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• 1985

The effect of anionic polyelectrolytes, poly(styrenesulfonate) (PSS) and poly(vinylsulfonate) (PVS), on the charge transfer complexing between indole derivatives and methyl viologen($MV^{++}$) cation was investigated. The results were compared with effect of NaCl and an anionic surfactant, sodium dodecylsulfate (SDS). Both PSS and PVS enhanced the complex formation of neutral species (indole and indole acetate at low pH), zwitter ionic tryptophan, and positively charged tryptamine and tryptophan at low pH with $MV^{++}$. This result was attributed to the contribution of hydrophobic interaction, in addition to electrostatic interaction. The enhancing effect of PSS was much higher than that of PVS reflecting the higher hydrophobicity of PSS. The interaction between indole acetate anion and $MV^{++}$ was greatly reduced by addition of PVS and PSS. The higher charge density of PVS was appeared as greater reducing effect indicating the importance of electrostatic force in this case. In all cases, the effect of polyelectrolytes showed maxima, and further addition of PVS and PSS decreased the effect. This behavior was explained in terms of distribution of indole derivatives and $MV^{++}$ in domain of polyanions. The complex formation constants and molar absorptivities of complexes were determined, and the values were compared with those in water and SDS solutions.

• 대한화학회지
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• 제53권3호
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• pp.257-265
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• 2009

$Cu^{+}$ 및 $Cu^{2+}$와 proline의 결합형태에 따른 구조 및 금속 친화도를 DFT(Density Functional Theory) 방법으로 조사하였다. 금속-proline의 결합과 여러 결합형태에 따른 에너지 순서는 $Cu^{+}$-Proline및 $Cu^{2+}$-proline 착화합물에서 서로 매우 상이함을 알았다. $Cu^{+}$-Proline의 경우, 바닥상태의 구조는 $Cu^{+}$가 중성 proline의 카르보닐 산소 및 이미노기 질소에 배위된 두 자리 배위를 하며, 이에 비해 $Cu^{2+}$-Proline 의 바닥상태의 구조는 zwitter이온 형태 proline의 카르복시기의 두 산소 사이에 chelation을 형성하는 구조임을 확인하였다. 가장 안정한 $Cu^{+}$-Proline 착화합물에서 proline의 금속 이온 친화도는 6-311++G(d,p) 수준에서 76.0 kcal/mol로 계산되었으며, proline의 $Cu^{2+}$ 이온 친화도는 258.5 kcal/mol로 나타났다.