• Bulletin of the Korean Chemical Society
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• v.18 no.5
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• pp.496-500
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• 1997

Electrochemical behavior of mer-tris(2-pyridinethiolato)cobalt(Ⅲ) in dimethylformamide was studied on a platinum electrode by means of cyclic voltammetry, chronoamperometry, and chronocoulometry. It was found that the neutral complex molecule was electroactive between the potential region of 1.0 and - 1.2 V vs. a nonaqueous Ag/Ag+ electrode. The Co(Ⅲ) complex was reversibly reduced to Co(Ⅱ) species by one-electron transfer at about - 1.1 V, followed by an irreversible dissociation reaction. However, the oxidation process at around 0.8 V, was responsible for an irreversible two-electron transfer that occurred at a ligand site.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2343-2353
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• 2007

We report the application of time-dependent density functional theory (TDDFT) to the calculation of potential energy profile relevant to the excited state intramolecular proton transfer (ESIPT) processes in title molecules. The TDDFT single point energy calculations along the reaction path have been performed using the CIS optimized structure in the excited state. In addition to the Stokes shifts, the transition energies including absorption, fluorescence, and 0-0 transition are estimated from the TDDFT potential energy profiles along the proton transfer coordinate. The excited state TDDFT potential energy profile of SA and 3ASA resulted in very flat function of the OH distance in the range ROH = 1.0-1.6 A, in contrast to the relatively deep single minimum function in the ground state. Furthermore, we obtained very shallow double minima in the excited state potential energy profile of SA and 3ASA in contrast to the single minimum observed in the previous work. The change of potential energy profile along the reaction path induced by the substitution of electron donating groups (-NH2 and -OCH3) at different sites has been investigated. Substitution at para position with respect to the phenolic OH group showed strong suppression of excited state proton dislocation compared with unsubstitued SA, while substitution at ortho position hardly affected the shape of the ESIPT curve. The TDDFT results are discussed in comparison with those of CASPT2 method.

• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.2023-2027
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• 2006

Dibenzyl sulfide was oxidized at the a-carbon to yield benzaldehyde in the presence of $Pd(NO_3)_2$. Oxygen itself could not oxidize the sulfide directly, instead the nitrato ligand of the palladium complex transferred oxygen to dibenzyl sulfide to form benzaldehyde. The X-ray crystal structure of the intermediate complex, cis-[$Pd(NO_3)_2${$S(CH_2C_6H_5)_2$}$_2$], revealed that the nitrato ligand was unidentate. Para-substituted dibenzyl sulfides I, $(YC_6H_4CH_2)_2S $wherein Y = $OCH_3$, $CH_3$, Cl, CN, or $NO_2$, were synthesized and reacted with palladium nitrate, and those with electron-donating substituents (Y = $OCH_3$ and $CH_3$) were good substrates for the oxidation reaction with palladium nitrate. Thus, the reaction mechanism of the oxygen transfer was proposed to include nucleophilic benzylic carbon.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.845-849
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• 1994

Tetracarbonylhydridoferrate, $HFe(CO)^-_4$, generated by the reaction of $Fe(CO)_5$ with alkaline solution, is a good reducing agent for mono-dehalogenation of gem-dihalocyclopropanes. It also acts as a good reducing catalyst under phase transfer reaction conditions. 1,1-Dibromo-2-phenylcyclopropane and 1,1-dichloro-2-phenylcyclopropane were reduced to the corresponding mono-dehalogenated products in excellent yields. Thermodynamically stable trans-l-bromo-2-phenyl cyclopropane was formed as the major product over the cis-isomer, trans/cis=3/2. The 1-bromo-2-phenyl cyclopropane radical intermediate was formed by single electron transfer from $HFe(CO)^-_4$. Dissociation of bromide anion, followed abstraction of hydrogen radical from alcoholic solvent would lead to the formation of the stable trans-isomer. The further mechanistic aspects were discussed.

• Journal of Electrochemical Science and Technology
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• v.10 no.2
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• pp.170-176
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• 2019

Alkanethiol self-assembled monolayers (SAMs) and partially ferrocene (Fc) modifications were applied to the Au ultramicroelectrode (UME) rather than to standard sized electrodes with dimension of millimeters. The electron transfer mediation of the SAMs and Fc modified Au UME was investigated by using a p-aminophenol (p-AP) oxidation reaction via cyclic voltammetry. The electrocatalytic p-AP oxidation at the SAMs and Fc modified Au UME showed a much larger electrocatalytic current density than that at the standard sized electrode due to the fast mass transfer rate at the UME.

• Environmental Sciences Bulletin of The Korean Environmental Sciences Society
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• v.10 no.S_3
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• pp.127-137
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• 2001

The sonochemical Process has been applied as a treatment method and was investigated its effect on the decomposition of humic substances(HS). The reaction kinetics and mechanisms in the Process of sonochemical treatment for humic substances(HS) in wastewater have also been discussed. It was observed that the metal ions such as Fe(II) and Mn(II) showed catalytic effects, while Al(III), Ca(II), and Mg(II) had inhibitory effects on the decomposition of humic substances in sonochemical reaction with hydrogen peroxide. Experimental results also showed factors such as hydrogen peroxide dose affected the formation of disinfection by-products. Two trihalomethanes, chloroform and dichlorobromomethane were formed as major disinfection by-products during chlorination. The mechanism of radical reaction is controlled by an oxidation process. The radicals are so reactive that most of them are consumed by HS radicals and hydroxyl radicals can be acted on organic solutes by hydroxyl addition, hydrogen abstraction, and electron transfer. The depolymerization and the radical reaction of HS radicals appear to occur simultaneously. The final steps of the reaction are the conversion of organic acids to carbon dioxide.

• Bulletin of the Korean Chemical Society
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• v.17 no.2
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• pp.179-182
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• 1996

Hydrodediazoniation product (3a-d) was found to be the major product in the reaction of arenediazonium tetrafluoroborate (1a-d) with triethylamine (2) in methanol under nitrogen at room temperature. A quantitative study on the title reaction was investigated in detail and two remarks were noteworthy. One was the linear increase in the yield of 3a-d by increasing the molar concentration of 2 until equimolar concentration was reached between 1a-d and 2. The other was the suppression of the formation of 3a-d in the presence of oxygen. Based on these results, the title reaction was better understood by 1:1 electron transfer reaction between reactants (1a-d and 2) rather than by radical chain mechanism proposed in the reaction of arenediazonium tetrafluoroborate and triphenylphosphine.

• Bulletin of the Korean Chemical Society
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• v.17 no.3
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• pp.269-273
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• 1996

Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠=28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.

• Journal of Photoscience
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• v.6 no.3
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• pp.91-96
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• 1999

Zeolites and microporouos materials continue to attract attention as novel hosts for photochemical reactions. Zeolities are attractive because of their ability to selectivity exchange and incorporate species within the void spaces and interconnecting channels, providing a spatial arrangement of molecules. Our research has primarily focused on intrazeolitic electron transfer from excited Ru(bpy)32+ in supercages of zeolite Y to a series of bipyridinium ions. In the Ru(bpy)32+ viologen-zeolite Y samples, the slowing of the back electron transfer from the bipyridinium radical cation to Ru(bpy)32+ allows for charge propagation via self exchange between diquat molecules. This provides an opportunity for permanent charge separation. When the migrating charge on the diquat radical within the zeolite reaches the surface, it can be transferred to a neutral viologen (PVS) in solution, resulting in permanent charge separation. The advantage of long-lived charge separation can be exploited for useful chemistry if suitable catablysts can be assembled on the zeolities. We have studied Ru(bpy)2 as water oxdiation catalysts. We have demonstrated that synthesis of RuO2 fibers on a zeolite via thermal decomposition of Ru3(CO)12 leads to the most active water decomposition catalyst reported to date. Because of the extensive interest of photochemical water reduction to H2, much is known about catalytic systems usin gone electron catalyst, and even more importantly, that no reaction of viologen occurred with H2 over this catalyst. The present challenge is to incorporate all these elements of the system into an architecture and we are examining zeolite membranes for this purpose.

• Bulletin of the Korean Chemical Society
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• v.7 no.2
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• pp.120-124
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• 1986

In order to investigate effective solar energy conversion system, the light-induced electron transfer reactions have been examined across single-lamellar liposomes incorporated organic photosensitizers such as anthracene and naphthalene derivatives. We have observed photosensitized reduction of methyl viologen (1,1'-dimethyl-4,4'-$bipyridinium^{2+}$) dissolved in the exterior aqueous phase of the pigmented phospholipid liposomes when EDTA, as electron donor, is dissolved in the enclosed aqueous phase of the liposomes. The anthroyl stearic acid incorporated in the hydrophobic bilayer of liposomes leads to much less quantum yield for the photosensitized reduction of $MV^{2+}$ than the anthracene carboxylate incorporated in the outer hydrophilic layer. However, ${\beta}$-carotene with anthroyl stearic acid incorporated into the bilayer enhances the quantum yield significantly (${\Phi}{\simeq}0.2-0.3$), preventing the reverse reaction of electron transfer ($MV^+_\ {\rightarrow}MV^{2+}$) so that it might be useful for solar energy conversion into chemical energy. A naphthalene derivative, octadecyl naphthylamine sulfonic acid incorporated into the outer layer of liposomes results in less efficiency of $MV^{2+}$ reduction than anthroyl stearic acid. These results have been also tested with respect to lipid components of liposomes.