• Nuclear Engineering and Technology
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• v.49 no.8
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• pp.1778-1782
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• 2017

The interaction of $NpO^+_2$ with $Cl^-$ was studied using visible-near-infrared spectroscopy in $NaCl-Ca-Cl_2-NaClO_4$, $NaCl-NaClO_4$, and $CaCl_2-NaClO_4$ solutions with ionic strength (I) of 6M. The spectra of $NpO^+_2$ around 980 nm varied with $Cl^-$ concentration in the $NaCl-CaCl_2-NaClO_4$ and $NaCl-NaClO_4$ solutions at [$Cl^-$] ${\geq}3.5M$, but not in the $CaCl_2-NaClO_4$ solution. Assuming the 1:1 interaction between $NpO^+_2$ and $Cl^-$, the apparent equilibrium constants at I = 6M were evaluated. The presence of $Ca^{2+}$ was found to destabilize overall interaction between $NpO^+_2$ and $Cl^-$. The observations were consistent with the density functional theory calculation.

• Journal of the Korean Chemical Society
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• v.24 no.2
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• pp.139-145
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• 1980

High spin iron(II) complexes of 1,4,8,11-tetraazacyclotetradecane (cyclam), a macrocyclic ligand, and 1,5,8,12-tetraazadodecane (3,2,3-tet), a noncyclic ligand, have been prepared. The reaction of low spin $[Fe(cyclam)(CH_3CN)_2](ClO_4)_2$ with chloride ion in methanol produces high-spin $[Fe(cyclam)Cl]ClO_4$. Although $[Fe(cyclam)(CH_3CN)_2](ClO_4)_2$ is low spin, $[Fe(3,2,3-tet)(CH_3CN)_2](ClO_4)_2$ isolated in the present study is high spin. This difference is explained in terms of the smaller constrictive effect exerted by the noncyclic ligand than the cyclic ligand. The isolation of $[Fe(cyclam)Cl]ClO_4$ provides evidences against the current view that the presence of either unsaturation or substituents on the macrocyclic ligands is necessary for the successful preparation of high spin five-coordinate iron (II) complexes. Reactions of $[Fe(cyclam)Cl]ClO_4\;and\;[Fe(3,2,3-tet)(CH_3CN)_2](ClO_4)_2$ with carbon monoxide yield low spin six-coordinate $[Fe(cyclam)Cl(CO)]ClO_4\;and\;[Fe(3.2,3-tet)(CH_3CN)(CO)](ClO_4)_2$, respectively.

• Korean Chemical Engineering Research
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• v.52 no.1
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• pp.92-97
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• 2014

Perchlorate ($ClO_4^-$) is an emerging contaminant of soil/groundwater and surface water. $ClO_4^-$ has been shown to inhibit iodide uptake into the thyroid gland and cause a reduction in thyroid hormone production. $ClO_4^-$ is highly soluble and very stable in water. Biodegradation by $ClO_4^-$-reducing bacteria (PRB) is considered the most important factor in natural attenuation of $ClO_4^-$. Rivers in an industrial complex have potential to be contaminated with $ClO_4^-$ discharged from point or non-point sources. In this study, water samples were taken from the rivers running through the Gumi industrial complexes and used for batch test to analyze $ClO_4^-$-degradation potential of river microorganisms. The results of 83-h batch culture showed that $ClO_4^-$-removal efficiency of all samples was 0.77% or less without addition of an external electron ($e^-$) donor. However $ClO_4^-$-removal efficiency was higher when an $e^-$ donor (acetate, thiosulfate, $S^0$, or $F^0$) was added into the batch culture, showing up to 100% removal efficiency. The removal efficiency was various depending on type of $e^-$ donor and site of sampling. When acetate was used as an $e^-$ donor, the highest $ClO_4^-$-removal efficiency was observed among the $e^-$ donors used in this study, suggesting that activity of heterotrophic PRB was dominant. The results of this study provide basic information on natural attenuation of $ClO_4^-$ by river microorganisms. The information can be useful to prepare a strategy to enhance efficiency of $ClO_4^-$ biodegradation for in situ bioremediation.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.679-684
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• 1992

New Pd(IV) complexes have been prepared through the reactions of $trans-[Pd(en)_2Cl_2](ClO_4)_2 $(en = ethylenediamine) with Guanine, Adenine, or Uracil anion as purine and pyrimidine base. We identified the ratio of central metal versus ligands by $C{\cdot}H{\cdot}N$ elemental analysis and proposed the coordinating site of the base by infrared spectrum, $^1H-NMR,\; and\; ^{13}C$-NMR spectrum. Guanine or Adenine ligand coordinated at N7 site and an en ligand exchanged for $ClO_4^-$ counter ions of the starting material . As these results, the complexes showed the formula $[Pd(en)L_2(ClO_4)_2](ClO_4)_2{\cdot}(en)$, (L = Guanine, Adenine). But in the Uracil complex no exchange of the en ligand and $ClO_4^-$ occured and Uracil anion preferred the N1 to N3 as coordinating site, the complex $[Pd(en)_2(Urac)_2](ClO_4)_2(Urac = Uracil anion).$

• Journal of the Korean Chemical Society
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• v.38 no.11
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• pp.808-818
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• 1994

The neutral compounds [$MCl_3L_2$(MeCN)] (M = Mo, V: L = $PPh_3$, 1/2 phda) have been prepared from the reaction of starting material $MCl_z$ (M = Mo; z = 5, M = V; z = 3) with N,P-donating ligands in acetonitrile solution. Addition of $AgClO_4$ to these neutral monomeric compounds in acetone solution were produced [$MCl_3-_nL_2(MeCN)(S)_n$]$(ClO_4)_n$ (n = 1, 2 : s = solvent). Finally treatment of bivalent cationic compound and neutral compound was formed chloride bridged dinuclear complex $[(MeCN)(L)_2ClM({\mu}-Cl)_2M'Cl(L)_2(MeCN)](ClO_4)_2$ and treatment of univalent cationic compound with half equivalent pyrazine to pyrazine bridged complex $[(MeCN)(L)_2Cl_2M({\mu}-pyz)M'Cl_2(L)_2(MeCN)](ClO_4)_2$. These complexes are characterized by elemental analysis, $^1H$, $^{13}C$ NMR, IR, Far-IR and UV-Vis spectroscopy.

• Journal of the Korean Chemical Society
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• v.27 no.5
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• pp.340-344
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• 1983

It has been found that both of the iridium (Ⅰ) complexes, Ir$(ClO_4$)(AN)(CO)$(Ph_3P)_2$(AN = $CH_2$CHCN, $Ph_3P = (C_6H_5)_3$P) and [Ir(AN)(CO)$(Ph_3P)_2]ClO_4$, react with $Cl^-$ to give IrCl(AN)(CO)$(Ph_3P)_2$, and [Ir(AN)(CO)$(Ph_3P)_2]ClO_4$ dissociates AN to yield Ir$(ClO_4)(CO)(Ph_3P)_2$ in the absence of excess AN added, and Ir$(ClO_4)(CO)(Ph_3P)_2$ reacts with $Cl^-$ to produce IrCl(CO)$(Ph_3P)_2$. It is suggested that the catalytic polymerization of AN with Ir$(ClO_4)(AN)(CO)(Ph_3P)_2$ proceeds through the formation of [(CO)(Ph_3P)_2$Ir(-CH=CHCN)(H)($CH_2$=CHCN)]Cl$O_4$ followed by the formation of iridium(alkyl)(alkenyl) type complex which undergoes a reductive elimination to produce the polymer of acrylonitrile.

• Journal of the Korean Chemical Society
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• v.37 no.7
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• pp.655-661
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• 1993

The neutral monomeric compounds $[Mo(NO)_2Cl_2(phen)]$ and $[W(NO)_2Cl_2(phen)]$ (phen= 1,10-phenanthroline) have been prepared by reactions of polymeric compounds $[{Mo(NO)_2Cl_2}n],\;[{W(NO)_2Cl_2}n]$ with chelate ligands. Additions of one equivalent of silver(I) perchlorate to these cis-dinitrosyl compounds in acetone solution produce $[Mo(NO)_2(phen)(S)Cl][ClO_4]\;and\;[W(NO)_2(phen)(S)Cl][ClO_4]$ (S = acetone). The homo- and hetero-dinuclear complexes, $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][ClO_4]_2$ (M = Mo, W) and $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][C1O_4]_2$ (M = Mo, M' = W) have been prepared by these monocationic complexes with pyrazine ligand respectively. These complexes characterized by elemental analysis, $1^H-\;and\;^{13}C-NMR$, infrared, and UV-visible spectroscopy are reported. The spectral data indicate that homo- and hetero-dinuclear complexes were symmetrical structures of $C_{2v}$.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1781-1786
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• 2007

Two copper(II) complexes, [CuL3](ClO4)2 bearing one N-CH2CH2CONH2 group as well as one N-CH2CH2CN group and [CuL4](ClO4)2 bearing two N-CH2CH2CONH2 groups, have been prepared by the selective hydrolysis of [CuL2](ClO4)2 (L2 = C-meso-1,8-bis(cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The complex [CuL5](ClO4)2 bearing one N-CH2CH2C(=NH)OCH3 and one N-CH2CH2CN groups has been prepared as the major product from the reaction of [CuL2](ClO4)2 with methanol in the presence of triethylamine. In acidic aqueous solution, the N-CH2CH2C(=NH)OCH3 group of [CuL5](ClO4)2 undergoes hydrolysis to yield [CuL6](ClO4)2 bearing both N-CH2CH2COOCH3 and N-CH2CH2CN groups. The crystal structure of [CuL5](ClO4)2 shows that the complex has a slightly distorted square-pyramidal coordination polyhedron with an apical Cu-N (N-CH2CH2C(=NH)OCH3 group) bond. The apical Cu-N bond distance (2.269(3) A) is ca. 0.06 A longer than the apical Cu-O (N-CH2CH2CONH2 group) bond of [CuL4](ClO4)2. The pendant amide group of [CuL3](ClO4)2 is involved in coordination. The carboxylic ester group of [CuL6](ClO4)2 is also coordinated to the metal ion in various solvents but is removed from the coordination sphere in the solid state.

• Journal of the Korean Chemical Society
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• v.39 no.7
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• pp.530-537
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• 1995

The neutral complexes $MCl_3(phda)(MeCN)]$ and $[MCl_3(PPh_3)_2(MeCN)]$ (M=Mo, V) were prepared by the reaction of $MCl_z$, (M=Mo; z=5, M=V; z=3) with N, P-donating ligands in acetonitrile solution. Addition of AgClO_4$ to these neutral monomeric complexes in acetone solution afforded $MCl_{3-n}L_2(MeCN)(S)_n](ClO_4)_n$ (n=1, 2 : s=solvent). Two types of asymmetrical homo- and hetero-dinuclear complexes have been synthesized. The type of chloride bridged dinuclear complex is $[(MeCN)(phda)ClM({\mu}-Cl)_2M'Cl(PPh_3)_2(MeCN)](ClO_4)_2.$ And the type of pyrazine bridged complex is $[(MeCN)(phda)Cl_2M({\mu}-pyz)M'Cl_2(PPh_3)_2(MeCN)](ClO_4)_2.$ These complexes were characterized by elemental analysis, $^1H,\;^13C$ NMR, IR, Far-IR and UV-Vis spectroscopy.

• Korean Chemical Engineering Research
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• v.48 no.2
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• pp.157-163
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• 2010

A new etchant formulation was developed in this study to increase the shadow mask production rate, utilizing the $Fe(ClO_4)_3$ as an additive in the aqueous $FeCl_3$ solution. The shadow mask etch rate increased substantially with the increase of $Fe(ClO_4)_3$ concentration in the etchant. The etch rate difference between Ni and Invar steel was also reduced with the addition of $Fe{(ClO_4)_3}$ for most of the operating conditions, which was caused by the enhanced etch rate of both Ni and Fe by the new etchant. The increase in etch rate with the addition of $Fe(ClO_4)_3$ to aqueous ferric chloride solution was attributed to the superior electron transfer capability of $ClO^{4-}$ ion to that of $Cl^-$ ion.