• 대한화학회지
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• 제28권6호
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• pp.384-392
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• 1984

완전히 포화된 거대고리 리간드의 Fe(II) 착화합물 [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$과 ([14]ane$N_4$:1,4,8,11-tetraazacyclotetradecane) 산소분자간의 반응을 아세토니트릴 용액중에서 연구하였다. [Fe([14]aneTEX>$_4)(CH_3CN)_2]^{2+}$는 산소와 쉽게 반응하여 낮은 스핀 Fe(III) 착화합물 [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$을 생성하고 이는 다시 산화성 탈수소 반응에 의해 낮은 스핀 Fe(II) 착화합물 [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$을 형성한다. [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$의 리간드는 불포화도가 매우 높고 이중결합이 컨쥬게이션 되어 있다. 또한 반응의 중간체로서 [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ 및 [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$도 분리되었다. 이 반응과 관련된 Fe(II) 착화합물들은 일산화탄소와 반응하여 [FeL(CH$_3CN)(CO)]^{2+}$ (L = 거대고리 리간드) 형태의 착화합물을 이룬다. [FeL(CH$_3CN)(CO)]^{2+}$의 $v_{CO}$ 값과 [FeL(CH$_3CN_2)^{2+}$의 Fe(II) ${\to}$ Fe(III)의 전기화학적 산화포텐셜 및 산소에 대한 정성적인 안전성은 거대고리 리간드의 불포화도가 높아질수록 증가한다.

• Bulletin of the Korean Chemical Society
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• 제16권11호
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• pp.1060-1064
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• 1995

The reactivity of superoxide ion (O2-.) with halogenated substrates is investigated by cyclic voltammetry and rotated ring-disk electrode method in aprotic solvents. The more positive the reduction potential of the substituted nitrile, the more facile is nucleophilic displacement by O2-.. The reaction rates of halogenonitriles with O2-. vary according to the leaving-group propensity of halide (Br > Cl > F). The relative reaction rates of other substituted nitriles are in the order of electron-withdrawing propensity of the substituent group (CN > C(O)NH2 > Ph ≒ CH2CN). The reaction of O2-. with dihalocarbons indicates that five-membered rings can be rapidly formed by the cyclization of substrate and O2-., and the relative rates of cyclization depend on the number of methylenic carbons {Br(CH2)nBr, [n=1 < 2 < 3 > 4 > 5]}. Mechanisms are proposed for the reaction of O2-. with halogenated substrates.

• 대한화학회지
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• 제68권3호
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• pp.139-145
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• 2024

This study aims to elucidate the mechanism involved in the hydrolysis of the hexacyanoferrate(III) complex ion (Fe(CN)₆^3-) and the mechanism leading to the formation of Prussian blue (Fe^III₄[Fe_II(CN)₆]₃·xH₂O, PB) in acidic aqueous solutions at moderately elevated temperatures. Hydrolysis constitutes a crucial step in generating PB through the widely used single-source or precursor method. Recent PB syntheses predominantly rely on the single-source method, where hexacyanoferrate(II/III) is the exclusive reactant, as opposed to the co-precipitation method employing bare metal ions and hexacyanometalate ions. Despite the widespread adoption of the single-source method, mechanistic exploration remains largely unexplored and speculative. Utilizing UV-vis spectrophotometry, negative-ion mode liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and a devised reaction, this study identifies crucial intermediates, including aqueous Fe^2+/3+ ions and hydrocyanic acid (HCN) in the solution. These two intermediates eventually combine to form thermodynamically stable PB. The findings presented in this research significantly contribute to understanding the fundamental mechanism underlying the acid-catalyzed hydrolysis of the hexacyanoferrate(III) complex ion and the subsequent formation of PB, as proposed in the sequential mechanism introduced herein. This finding might contribute to the cost-effective synthesis of PB by incorporating diverse metal ions and potassium cyanide.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2043-2048
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• 2014

Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[$10.2.2^{5.8}$]-octadecane ($L^2$) containing additional N-$CH_2CH_2$-N linkages, C-meso-$L^2$ and C-racemic-$L^2$, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-$L^1$ or C-racemic-$L^1$ ($L^1$ = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-$L^2$ and C-racemic-$L^2$ react with copper(II) ion to form $[Cu(C-meso-L^2)]^{2+}$ or $[Cu(C-racemic-L^2)]^{2+}$ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) ${\AA}$] of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ are longer than those [1.992(3)-2.000(3) ${\AA}$] of [Cu(C-racemic-$L^1$)($H_2O$)]$(ClO_4)_2$. As a result, $[Cu(C-racemic-L^2)(H_2O)]^{2+}$ exhibits weaker ligand field strength than $[Cu(C-racemic-L^1)(H_2O)]^{2+}$. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex $[Cu_2(C-meso-L^2)_2CN]^{3+}$ or $[Cu_2(C-racemic-L^2)_2CN]^{3+}$. Spectra and chemical properties of $[Cu(C-meso-L^2)]^{2+}$ and $[Cu_2(C-meso-L^2)_2CN]^{3+}$ are not quite different from those of $[Cu(C-racemic-L^2)]^{2+}$ and $[Cu_2(C-racemic-L^2)_2CN]^{3+}$, respectively.

• 분석과학
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• 제14권6호
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• pp.540-544
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• 2001

Determination of cyanide ion has been studied by adsorptive stripping voltammetry using hanging mercury electrode. Cyanide ion complexed with copper ion is adsorpbed on the electrode and oxidised at the positive potential scan. Optimal conditions of CN determination were found to be ; supporting electrolyte solution ; 0.1 M NaCl of ammonium buffer at pH 10, accumulation potential; -800 mV vs Ag/AgCl, accumulation time ; 300 s, scan rate ; 50mV/s. The linear concentration of cyanide ion was observed in the range $1{\times}10^{-8}$, $1{\times}10^{-7}M$. The detection limit(n/s=3) was $0.13{\mu}g/L$($5{\times}10^{-9}M$) with 3.5% RSD.

• 대한의용생체공학회:의공학회지
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• 제25권2호
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• pp.157-163
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• 2004

금속 임플란트 재료들의 마모저항을 향상시키기 위하여 질소 이온주입 및 이온도금 기술을 적용하였다. 질소 이온주입 된 초내식성 스테인리스강(S.S.S)의 마모이온용출 특성을 S.S.S, 316L SS, TiN코팅된 316S SS와 비교 평가하기 위하여 탄소로 원자흡수분광분석기를 이용하여 시편들로부터 마모용출된 Cr과 Ni 이온량을 측정하였다. 또한, 저온아크증착법을 이용하여 TiN, ZrN, TiCN코팅된 Ti(Grade 2)원반의 마모저항을 비교하였고, 질소이온주입 및 질화물 코팅된 표면충의 화학적 조성은 SAES(scanning Auger electron spectroscopy)를 이용하여 분석하였다. 질소 이온주입된 S.S.S 표면으로부터 마모에 의하여 용출된 Cr과 Ni 이온량은 표면처리하지 않은 스테인리스강들에 비하여 크게 감소하였다 그러나 인공고관절에 걸리는 하중조건 하에서 실행된 마모이온용출실험에서 이온에너지 100 KeV로 질소이온 주입된 표면층은 20만회 내에서 쉽게 제거되었다. 질화물 코팅된 Ti 시편들의 마모저항도 크게 향상되었고, 그 마모특성은 코팅층의 화학적 조성에 따라 크게 차이가 났다. 코팅두께 3Um의 코팅시편들 중 TiCN 코팅된 티타늄이 가장 높은 내마모 특성을 보였으나 같은 하중조건 하에서 disk(Ti)-on-disk 마모실험에서 그 질화물 코팅면들의 마모 무게감 소비는 1만회 아래에서 모두 Ti의 마모비와 유사하게 전환되었다. 본 실험으로부터 얻어진 연구결과에 의하면, 100 KeV 질소이온주입 및 두께 3$\mu\textrm{m}$의 길화코팅된 표면층의 경우 표면 경화충의 깊이가 충분치 않아 높은 하중을 받는 임플란트의 마찰부위에 사용하기에는 한계가 있음을 보였다.

• 한국환경보건학회지
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• 제14권2호
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• pp.65-71
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• 1988

In this study, the method of adsorption by activated carbon in the removal of Hg(II) ion in waste water was treated. The influence of kinds of activated carbon and effect of temperature and the influence of coexistent salt on adsorption rates, the influence of pH in the adsorption, equilibrium and adsorption of mercury from activated carbon were investigated. From the adsorption on activated carbon of mercury(II) ion in the presence of cyanide or thiocyanate ion was found that mercury(II) was easily adsorved onto the activated carbon in the form of complex artion such as Hg(CN)$_4^{2-}$, Hg(SCN)$_4^{2-}$ respectively. ZnCl$_2$ activation method had a higher adsorptive ability than steam activation method in adsorption of Hg on activated carbon. Activated carbon adsorbed iodide ion is very effective on adsorption of Hg.

• 대한화학회지
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• 제24권2호
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• pp.139-145
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• 1980

마크로사이클리간드인 1,4,8,11-테트라아자사이클로테트라데칸 (cyclam)과 비환형 리간드인 1,5,8,12-테트라아자도데칸 (3,2,3-tet)의 높은 스핀철(Ⅱ) 착화합물이 합성되었다. 낮은 스핀인 $[Fe(cyclam)(CH_3CN)_2](ClO_4)_2$는 메탄올속에서 염소이온과 반응하여 높은 스핀인 $[Fe(cyclam)Cl]ClO_4$를 생성한다. $[Fe(cyclam)(CH_3CN)_2](ClO_4)_2$는 낮은 스핀이지만 $[Fe(3,2,3-tet)(CH_3CN)_2](ClO_4)_2$는 높은 스핀을 가지며 이 차이는 비환형 리간드가 환형 리간드보다 압축효과가 작은 것으로 설명된다. $[Fe(cyclam)Cl]ClO_4$의 합성은 마크로사이클리간드가 불포화되어 있거나 치환체가 있어야 높은 스핀 다섯배위철(II) 착화합물의 합성이 가능하다는 지금까지의 전해에 반대되는 증거가 된다. $[Fe(cyclam)Cl]ClO_4$와 $[Fe(3,2,3-tet)(CH_3CN)_2](ClO_4)_2$는 일산화탄소와 반응해서 각기 낮은 스핀 여섯배위인 $[Fe(cyclam)Cl(CO)]ClO_4$ 와 $[Fe(3.2,3-tet)(CH_3CN)(CO)](ClO_4)_2$를 만든다.

• 한국산업융합학회 논문집
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• 제19권4호
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• pp.198-205
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• 2016

For the study on the ion exchange of nickel hexacyanoferrate(NiHCNFe) electrode with the several cations, the film of hexacyanoferrate was prepared on the bare nickel surface by the electrochemical and chemical methods in the solution composed with 5mM K3Fe(CN)6 and 100mM KNO3. To compare the capability of the ion exchange of NiHCNFe film electrode, the repeated cyclic voltammograms were measured in the 0.5M cation nitrate solutions at $25^{\circ}C$ and pH7. It was found that the capacity of the electrochemically derivatized NiHCNFe reduced in the rate of 0.5~0.7%/cycle and was nearly exhausted at the 150th potential cycle. Better result was obtained from that the capacity loss of the chemically assembled NiHCNFe was less than 0.02%/cycle for 5,000cycles. Furthermore, the residual capacity was more than 30% at the 5,000th cycle.

• Bulletin of the Korean Chemical Society
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• 제31권3호
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• pp.689-693
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• 2010

Second-order rate constants ($k_{CN^-}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-r) with $CN^-$ ion in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot is linear with ${\beta}_{1g}$ = -0.49, a typical ${\beta}_{1g}$ value for reactions reported to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^{\circ}$ and ${\sigma}^-$ constants exhibit many scattered points. In contrast, the Yukawa-Tsuno plot for the same reaction exhibits excellent linearity with ${\rho}_Y$ = 1.37 and r = 0.34, indicating that a negative charge develops partially on the oxygen atom of the leaving aryloxide in the rate-determining step (RDS). Although two different mechanisms are plausible (i.e., a concerted mechanism and a stepwise pathway in which expulsion of the leaving group occurs at the RDS), the reaction has been concluded to proceed through a concerted mechanism on the basis of the magnitude of ${\beta}_{1g}$ and ${\rho}_Y$ values.