• Bulletin of the Korean Chemical Society
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• 제13권5호
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• pp.556-559
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• 1992

Hydrocarbon solution of $(PPh_3)_2(CO)MOSO_2CF_3$ (M= Rh, Ir) reacts rapidly with 1,4-dicyanobenzene or 1,4-dicyano-2-butene to yield dinuclear metal complexes $[(PPh_3)_2(CO)M({\mu}-dicyanobenzene)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (I: M = Rh; II: M = Ir) or $[(PPh_3)_2(CO)M({\mu}-dicyano-2-benzene)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (III: M = Rh; IV: M = Ir), respectively. Compounds I, II, III, and IV were characterized by $^1H$-NMR, $^{31}P$-NMR, and infrared spectrum. Dichloromethane solution of II and IV reacts with $H_2\;and\;I_2$ to yield oxidative addition complexes $[(PPh_3)_2(CO)IrX_2({\mu}-E)X_2Ir(CO)(PPh_3)_2](SO_3CF_3)_2$ (V; E = 1,4-dicyanobenzene, $X_2$ = $H_2$; VI : E = 1,4-dicyano-2-butene, $X_2$ = $H_2$; VII; E = 1,4-dicyanobenzene, $X_2$ = $I_2$). All metal complexes are bridged by the cyanide groups. Compounds Ⅴ, Ⅵ, and Ⅶ are characterized by conventional methods.

• Bulletin of the Korean Chemical Society
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• 제20권6호
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• pp.648-652
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• 1999

Studies have been carried out on the unusual molecular nonrigidity of CoⅢ(PymS)3 and Cp* RhⅢ(PymS)2(PymS:2-mercaptopyrimidine). The crystal structure of CoⅢ(PymS)3 approximates to an octahedral mer isomer with 4-membered N-Schelating fashion. For Cp*RhⅢ(PymS)2, one PymS ligand bonds to the rhodium ion in an S-monodentate mode (Rh-S(2) = 2.366(1)Å) while the other ligand chelates to the metal ion in an N,S-bidentae mode (Rh-S(1)=2.414(1);Rh-N(1)=2.103(3)Å). Even though the conformations and configurations of both complexes are still retained in solution, an unusual nonrigidity for the protons of the PymS region is obsered in the solution. The broad proton signals of CoⅢ(PymS)3 exhibit a temperature-dependence in the range of -40∼40℃ with a free energy of activation ΔG=64.49kJ/mol(40℃). For Cp*RhⅢ(PymS)₂,such a fluxionality has been markedly observed in solution. This fluxional behavior can be explained in terms of "ligand tautomerism" in metal complexes containing potential tautomeric forms.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.218-224
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• 2014

In order to explore new coordination frameworks with novel designed 3-nitrophthalic acid and the same N-donor ancillary ligand, a series of novel coordination complexes, namely, $[Cd_2(3-NPA)_2(TBZ)_2(H_2O)_2]{\cdot}2H_2O$(1), $[Zn_2(3-NPA)_2(TBZ)_2]$(2), $[Zn_2O(3-NPA)(TBZ)(H_2O)]_n$(3), $[Co(3-NPA)(TBZ)(H_2O)]_n$(4) (3-$NPAH_2$ = 3-nitrophthalic acid), have been hydrothermally synthesized through the reaction of 3-nitrophthalic acid with divalent transition-metal salts in the presence of N-donor ancillary coligand (TBZ = thiabendazole). As a result of various coordination modes of the versatile 3-$NPAH_2$ and the coligand TBZ, these complexes exhibit structural diversity. X-ray structure analysis reveals that 1 and 2 are 0D molecular rings, while 3 and 4 are one-dimensional (1D) infinite chain polymers. And the weak O-H${\cdots}$O hydrogen bonds and C-H${\cdots}$O nonclassical hydrogen bonds as well as ${\pi}-{\pi}$ stacking also play important roles in affecting the final structure where complexes 1, 3 and 4 have 3D supramolecular architectures, while complex 2 has a 2D supramolecular network. Also, IR spectra, fluorescence properties and thermal decomposition process of complexes 1-4 were investigated.

• 대한화학회지
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• 제17권6호
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• pp.416-423
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• 1973

양이온 교환수지(Ion Exchange Resin CGC 241)와 2염기산인 말론산 혹은 프탈산이온이 들어있는 용액에서 방사성 알칼리토류금속 이온이 수지와 용액사이에 어떻게 분배되는가를 실온에서 조사함으로써 알칼리토류금속의 유기산 착물 형성에 관한 연구를 하였다. 용매로서 H2O, 20% 에탄올-물 및 20% 아세톤-물을 사용하였고, 용액의 pH는 7.2∼7.5로 조절하였고, 이온강도는 0.10∼0.11fh 유지하였다. 본 연구결과 알칼리토류금속 이온과 말론산 및 프탈산 사이에 1:1착물이 모든 용매계에서 형성되었고 착물의 안정도는 다음순으로 증가됨을 알았다. $Ba^{++}\;<\;Sr^{++}\;<\;Ca^{++}$, 말론산 < 프탈산, 수용액 < 혼합용매

• 한국토양비료학회지
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• 제49권5호
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• pp.589-597
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• 2016

There are a number of industrial complexes which could be a source of heavy metal (loid)s contamination of arable soil in Gyeongnam province of South Korea. Heavy metal (loid)s accumulation of plant is more related to the concentration of plant available heavy metal (loid)s in arable soil than that of total heavy metal (loid)s. The objectives of this study were 1) to examine heavy metal concentrations in soils located near industrial complexes in Gyeongnam province and 2) to determine the relationship between concentration of plant available heavy metal (loid)s and chemical properties of soil. Soil samples were collected from 85 sites of arable lands nearby 7 industrial complexes in Gyeongnam province. Total heavy metal (loid)s concentration, available heavy metal (loid)s concentration, and chemical properties of collected soils were measured. The mean concentrations of arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) in the soils were $5.8mg\;kg^{-1}$, $1.3mg\;kg^{-1}$, $0.03mg\;kg^{-1}$, $51.5mg\;kg^{-1}$, and $68.7mg\;kg^{-1}$, respectively. Total concentration of Cd and Zn in arable soil located near ${\nabla}{\nabla}$ industrial complex exceeded the warning criteria ($4mg\;kg^{-1}$ and $300mg\;kg^{-1}$ for Cd and Zn, respectively) as described by in the soil environmental conservation Act of Korea. The concentration of plant available heavy metal (loid)s was negatively related to the soil pH and available Pb and Zn concentrations had relatively high correlation coefficient when compared with other heavy metal (loid)s. The concentration of plant available Pb and Zn was negatively related to that of organic matter (OM). Based on the above results, it might be a good soil management to control pH and OM concentration with soil amendments such as lime and compost to reduce phytoavailability of heavy metal (loid)s in arable soil located near industrial complex.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3321-3330
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• 2012

The complexation characteristics of mixed [2 + 2'] calix[4]aryl derivatives (3 and 4) with alkali metal cations were investigated by the mPW1PW91 (hybrid HF-DF) calculation method. The total electronic and Gibbs free energies of the various complexes (cone, partial-cone, 1,2-alternate, and 1,3-alternate) of sodium and potassium cations with 3 and 4 were analyzed and compared. The structures of the endo- or exo-complexes of the alkali metal cation with the host 3 were optimized using the mPW1PW91/6-31G(d) method, followed by mPW1PW91/6-311+G(d) calculations. The structures of the endo- or exo-complexes of the alkali metal cation with the host 4 were optimized using the mPW1PW91/6-31G(d,p) method. The mPW1PW91 calculated relative energies of the various conformations of the free hosts (3 and 4) suggest that the cone conformers of 3 and 4 are the most stable. The mPW1PW91calculations also suggest that the complexation efficiencies of the sodium ion with hosts 3 and 4 are about 24 and 27 kcal/mol better than those of the potassium ion, respectively. These trends are in good agreement with the experimental results. The exo-complexation efficiencies of the sodium ion toward the conformers of hosts 3 and 4 are roughly 14 and 17 kcal/mol better than those for the endo-$Na^+$-complexes of 3 and 4, respectively. The exo-complexation of the cone isomer of 3 with cation could be confirmed by the differences of the diagnostic C=O bands in the free host and its complex's IR spectra.

• 분석과학
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• 제11권6호
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• pp.440-447
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• 1998

브롬 치환기를 가지는 여러자리 시프염기인 5-Br-BSDT(bis(5-bromosalicylaldehyde)diethy- lenetriamine), 5-Br-BSTT(bis(5-bromosalicylaldehyde)triethylenetetramine)와 5-Br-BSTP(bis(5-bromosalicylaldehyde)tetraethylenepentamine)를 합성하여 DMSO 용매에서 이들 리간드들과 구리(II), 니켈(II) 및 아연(II) 등의 전이금속과의 안정도 상수값을 폴라로그래피를 이용하여 구하였다. 이때 금속과 리간드는 1 : 1착물을 형성하였고, 안정도 상수값은 금속으로서는 Cu(II)>Ni(II)>Zn(II) 순서로, 리간드로서는 5-Br-BSTP>5-Br-BSTT>5-Br-BSDT 순서로 나타남으로서 주개 원자수의 증가에 의존한다는 사실을 알았다. 엔탈피와 엔트로피는 모두 음의 값을 나타내었는데 흡열반응으로서 금속이온과 리간드가 매우 강하게 결합하고 있음을 알 수 있고 극성을 가지는 금속착물이 생성되어 용매인 DMSO와 아주 강한 상호작용을 함으로써 큰 음의 엔트로피 값을 가진 것으로 생각된다.

• 대한화학회지
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• 제15권4호
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• pp.199-203
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• 1971

The adsorption method for the determination of the formation constants of the metal complexes with organic acids was developed by using membrane filters. The adsorption method involved the measurements of radioactivities of the adsorbed metal on membrane filters and the filtrate solution after the radioactive metal ion were filtered through membrane filters in the presence of organic ions of varying concentration. Comparing the adsorption method with the ion exchange method, it was seen that the adsorption method was simpler and faster than the ion exchange method. As an example of the metal complex with organic acid yttrium citrate complex was chosen, and the formation constant of the complex obtained by the adsorption method showed $K_f=2.0{\times}10^{-4}(l. mole^{-1})$ at a pH of 7. Also the present study revealed that the carrierfree state of yttrium in aqueous solution was present in the completely ionized state.

• Bulletin of the Korean Chemical Society
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• 제15권9호
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• pp.766-771
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• 1994

A number of molybdenum(VI), -(V), and -(IV) oxo complexes with S-methyl 3-(2-hydroxyphenyl)methylenedithiocarbazate and its derivatives as the ONS-donor metal-binding substrate are synthesized. The Mo(VI)-dioxo complexes are cis-dioxo Mo$O_2$L(D), where D is solvent molecules such as MeOH, DMF, Py(pyridine), DMSO, and ${\gamma}$-Pic(${\gamma}$-picoline). The Mo(V)-oxo complexes are of the type (PyH)[MoO(NCS$)_2$L] with an octahedral geometry. The Mo(IV)-oxo complexes, MoOL are derived from corresponding Mo(VI)-dioxo complexes by oxo abstraction with PP$h_3$. The complexes are characterized by IR, $^1$H-NMR, UV-Vis spectroscopy and cyclic voltammetry. On the basis of ligand displacement reaction, the qualitative order of D binding for Mo$O_2$L(D) complexes is also discussed.

• 농업과학연구
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• 제46권4호
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• pp.799-811
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• 2019

The aim of this study was to evaluate heavy metal contamination and pollution index of agricultural soils around industrial complexes in the Jeon-Buk Regions of Korea. Soil samples near industrial complexes in 2017 were collected at two depths (0 - 15 and 15 - 30 cm) within a 500- and 1000-meter radius before planting. Eight heavy metals (Arsenic (As), cadmium (Cd), chromium (Cr), Cupper (Cu), nickel (Ni), lead (Pb), mercury (Hg) and zinc (Zn)) and the pollution index (PI), geoaccumulation index (Igeo) and soil pollution index (SPI) were evaluated based on soil contamination warning standard (SCWS). Overall, the heavy metal concentrations were below the SCWS. The PI ranged from 0.1 to 0.9 and categorized into Group 1 which is not polluted with any heavy metals. The average Igeo values of all the soil samples ranged from - 2.56 to 3.22. The Igeo values of Cd and Hg may not represent well the pollution index because the heavy metal concentrations in the soil is lower compared to the SCWS. In fact, based on the heavy metal concentrations, the Igeo for monitored soils should be categorized into Group 1, uncontaminated to moderately contaminated. However, the Igeo of Cd and Hg are classified into heavily contaminated. These results suggest that for calculating the Igeo, the heavy metal concentration and background concentration should be used very carefully if the heavy metal concentration in the soil is lower than the background concentration. SPI for all the soil samples ranged from 0.00 to 0.11 which indicates no heavy metal pollution was observed.