• Bulletin of the Korean Chemical Society
• /
• 제23권8호
• /
• pp.1062-1066
• /
• 2002

The complexes [Ni(L)(INT)2]${\cdot}$5H2O (1) and [Cu(L)(H2O)](Cl)(INT)${\cdot}$3H2O (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18 ,07.12 ]docosane, INT = isonicotinate) have been prepared and characterized by X-ray crystallography, electronic absorption, and cyclic voltammetry. The crystal structure of 1 reveals an axially elongated octahedral geometry with two axial isonicotinate ligands. The electronic spectra, magnetic moment, and redox potentials of 1 also show a high-spin octahedral geometry. However, 2 shows that the coordination environment around the copper atom is a distorted square-pyramid with an axial water molecule. The spectra and electrochemical behaviors of 2 are also discussed.

• Bulletin of the Korean Chemical Society
• /
• 제33권8호
• /
• pp.2517-2522
• /
• 2012

New polynuclear poly(hexaaza macrocyclic) copper(II) complexes $[1](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, $[2](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, and $[3](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$ have been prepared by the one-pot reaction of formaldehyde with ethylenediamine and 1,2-bis(2-aminoethoxy)ethane, 1,3-diaminopropane, or 1,6-diaminohexane in the presence of the metal ion. The polymer complexes contain fully saturated 14-membered hexaaza macrocyclic units (1,3,6,8,10,13-hexaazacyclotetradecane) that are linked by $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-N$, $N-(CH_2)_3-N$, or $N-(CH_2)_6-N$ chains. The mononuclear complex $[Cu(H_2L^5)](ClO_4)_4$ ($H_2L^5$ = a protonated form of $L^5$) bearing two $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-NH_2$ pendant arms has also been prepared by the metal-directed reaction of ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, and formaldehyde. The polymer complexes were characterized employing elemental analyses, FT-IR and electronic absorption spectra, molar conductance, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron micrograph (SEM). Electronic absorption spectra of the complexes show that each macrocyclic unit of them has square-planar coordination geometry with a 5-6-5-6 chelate ring sequence. The polymer complexes as well as $[Cu(H_2L^5)]^{4+}$ are quite stable even in concentrated $HClO_4$ solutions. Synthesis and characterization of the polynuclear and mononuclear copper(II) complexes are reported.

• 대한화학회지
• /
• 제32권2호
• /
• pp.122-129
• /
• 1988

$Co(sp)X_2P$(sp=sparteine, $C_{15}H_{26}N_2$, X=Cl, Br)과 Cu(sp)$X_2$의 아쿠오화반응이 메카니즘을 규명하기 위하여 pH~5인 조건에서 속도론적 연구를 실시하였다. Co(sp)$Cl_2$ 및 $Co(sp)Br_2$는 halide 이온들에 의해 촉매 효과를 나타내지 않았으며 $Cu(sp)Cl_2$ 및 $Cu(sp)Br_2$에 비해 매우 빠르게 아쿠오화가 진행되었다. $Cu(sp)Cl_2$ 및 $Cu(sp)Br_2$는 halide cyanide의 존재에 의해 반응속도가 크게 증가하였으며 pH = 2~5인 범위에서 pH가 증가함에 따라 반응속도가 증가하였다. 본 연구에서 얻어진 실험결과, $Co(sp)X_2$의 아쿠오화반응이 D-메카니즘으로 진행되는 반면 $Cu(sp)X_2$의 경우는 $I_d$ 메카니즘으로 진행되는 것으로 믿어진다.

• 대한화학회지
• /
• 제39권12호
• /
• pp.932-939
• /
• 1995

시프 염기 구리(II) 착물에 의한 과산화수소 분해속도를 측정하였다. 과산화수소와 구리(II)-시프염기 착물의 반응속도는 $Cu^{II}BSDT$ 및 $Cu^{II}BSTP$인 경우 pH에 따라 증가하였으나 $Cu^{II}BSTT$의 경우 증가하였다가 감소하였다. 이 반응의 메카니즘은 과산화수소의 시프염기 구리(II) 착물의 탈양성자를 거친 다음에 속도결정단계에서 퍼옥소 구리착물이 생성되는 반응과정과 일치한다.

• Bulletin of the Korean Chemical Society
• /
• 제24권3호
• /
• pp.269-273
• /
• 2003

The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

• Bulletin of the Korean Chemical Society
• /
• 제12권3호
• /
• pp.276-281
• /
• 1991

Electrochemical behaviors of optically active sparteine-Cu(II) dihalide complexes were investigated by polarography and cyclic voltammetry (CV). These Cu(II) complexes are rather easier to be reduced to Cu(I) states when comparison is made with other nonplaner copper complexes, We have assigned the CV peaks and polarographic waves related to the redox processes for these complexes. We could also observe the exchange reaction of Cu(II) ion in the complex with mercury metal in the cell having mercury pool. The redox mechanism of these complelxes is as follows; The 1st wave appeared at +0.47 V/+0.65 V corresponds to the reaction of $SpCuX_2+ e{\rightleftarrow}SpCuX_{2^-}$ and the 2nd one at +0.26 V/+0.21 V does the reaction of $SpCuX_{2 ^-} +e{\rightleftarrow}SpCuX_2^{2-}$. The 3rd one at -0.35 V/-0.27 V is dueto the reduction of mercury complex formed via exchange reaction. Where, X is chloride ion.

• Bulletin of the Korean Chemical Society
• /
• 제10권4호
• /
• pp.362-366
• /
• 1989

Square planar nickel(II) and copper(II) complexes of 14-membered macrocyclic ligands containing various alkyl pendant arms at the uncoordinated nitrogen atoms, 1,8-dipropyl, 1,8-dibutyl, 1,8-bis(2-methylpropyl), 1,8-bis(2-ethylhexyl), and 1,8-dibenzyl-1,3,6,8,10,13-hexaazacyclotetradecane have been prepared from the template condensation of ethylenediamine, formaldehyde, and appropriate primary amines in the presence of the metal ion. The spectroscopic and electrochemical properties of these complexes are similar to those of tetraaza macrocyclic complexes and are not affected significantly by the nature of the alkyl groups.

• Bulletin of the Korean Chemical Society
• /
• 제29권9호
• /
• pp.1711-1716
• /
• 2008

The reaction of copper(II) chloride with phenyl-N-[(pyridine-2-yl)methylene]methaneamide (ppmma) leads to a new $\mu$ -chloro bridged dimeric [Cu(ppmma)$Cl_2$]$_2$ complex, whereas a reaction of copper(II) bromide with ppmma affords a monomeric Cu(ppmma)$Br_2$ complex. Both complexes have been characterized by X-ray crystallography and electronic absorption spectroscopy. The crystal structural analysis of [Cu(ppmma)$Cl_2$]$_2$ shows that the two Cu(II) atoms are bridged by two chloride ligands, forming a dimeric copper(II) complex and the copper ion has a distorted square-pyramidal geometry ($\tau$ = 0.2). The dimer units are held through a strong intermolecular $\pi-\pi$ interactions between the nearest benzyl rings. On the other hand, Cu(ppmma)Br2 displayed a distorted square planar geometry with two types of strong intermolecular π-π interaction. EPR spectrum of [Cu(ppmma)$Cl_2$]$_2$ in frozen glas s at 77 K revealed an equilibrium between the mononuclear and binuclear species. The magnetic susceptibilities data of [Cu(ppmma)$Cl_2$]$_2$ and Cu(ppmma)$Br_2$ follow the Curie-Weiss law. No significant intermolecular magnetic interactions were examined in both complexes, and magnetic exchange interactions are discussed on the basis of the structural features.

• 청정기술
• /
• 제19권4호
• /
• pp.487-491
• /
• 2013

Dowex21K XLT 수지에 흡착된 금과 구리-시안 착화합물을 효과적으로 탈착시키기 위하여 쌍극성의 반 양성자성 용매의 일종인 아세톤을 염산과 섞은 혼합용매를 탈착제로 이용하였다. 염산과 아세톤의 혼합비율(부피비)이 7:3일 때 금-시안 착화합물의 탈착율은 약 94%로서 가장 높았으나 아세톤의 비율이 증가할수록 금-시안 착화합물의 탈착율은 감소하였다. 구리-시안 착화합물의 경우는 염산의 비율이 아세톤의 비율보다 상대적으로 높았을 때 거의 대부분을 탈착시켰으나 아세톤의 비율이 증가할수록 탈착율은 감소하였다. 또한, 0.6 M의 염산을 사용하였을 때(염산과 아세톤의 혼합비율은 7:3으로 고정) 금과 구리-시안 착화합물의 탈착율은 각각 94%와 100%였으며 더 높은 염산 농도를 사용하여도 금-시안 착화합물의 탈착율은 증가하지 않았다. 그리고 고체와 액체의 비(ratio of solid and liquid)가 1.0보다 작을 때는 금과 구리-시안 착화합물 모두 100%의 탈착율을 보여주었으나 1.0보다 클 때에는 금-시안 착화합물의 탈착율이 약 20~29%로서 아주 낮았다. 또한, 금과 구리-시안 착화합물에 대한 대부분의 탈착공정은 120분 내에 이루어졌다.

• 대한화학회지
• /
• 제55권4호
• /
• pp.603-611
• /
• 2011

Ethoxylacetyl oxime 리간드 [HL, (1) 및 $H_2L^1$, (3)]와 아세트산 구리(II) 일수화물을 반응시켜 팔면체 및 사각평면착물을 각각 얻었다. 이들 착물을 원소분석, IR 및 UV-Vis 스펙트럼, 자기수자율, 전기전도도 및 ESR 스펙트럼으로 조사하였다. DMF에서 이들 착물의 몰전기전도도 측정한 결과 비이온성을 보였다. 실온 및 77 K에서 [$(L)_2Cu(H_2O)_2$], (2) 착물의 ESR 스펙트럼은 배위결합성을 갖는 축대칭($d_{x2-y2}$)의 특성을 보이며, 또한 전형적인 쌍극자 상호작용에 의해 큰 띠나비를 갖는다. 그러나 착물 [$(L^1)Cu$], (4)는 고체상태에서 큰 띠넓임으로 인해 초미세 갈라짐이 관찰되지 않았는데, 이는 구리(II) 결합자리들 사이의 스핀-교환 상호작용에 의한 것으로 확인되었다. 실온에서 도포된 구리(II) 착물의 스펙트럼은 배위된 질소원자로 인해 극초미세 갈라짐을 보였다. 또한 이 물질은 공유 결합성을 갖는 축형태($d_{x2-y2}$)의 특성을 보이고, 구리(II) 이온의 환경은 기본적으로 사각-평면 배열을 갖는다. 77 K의 얼어있는 메탄올에서 [$(L_1)Cu$], (4)의 스펙트럼은 이합체 화합물의 삼중항 상태의 특성을 보이며, 두 구리(II) 이온 중심 사이의 거리를 계산한 결과 4.8 이다.