• Title/Summary/Keyword: Cu-NO complexes

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The Availability of Automobile Catalytic Convert of Copper Based on the DFT Calculations of Cu-NO Complexes (Cu-NO 복합체에 대한 DFT 계산에 따른 Cu의 자동차 촉매변환기 적합성)

  • Ha, Kwanga;Lee, Min-Joo
    • Journal of the Korean Chemical Society
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    • v.62 no.5
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    • pp.358-363
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    • 2018
  • The purpose of this study is to show the possibility of using Cu catalyst in removal of $NO_x$ from automobile exhaust which is regarded as the primary source of fine dust PM2.5. The energy and the bond lengths of the three possible structures of Cu-NO complex, which is formed by binding NO molecule to Cu, and the changes in IR and Raman spectra are calculated using MPW1PW91 method on the level of 6-311(+)G(d,p) of basis sets with Gaussian 09 program. As a result, the enthalpy of formation of the Cu-NO complexes are obtained as ${\Delta}H=104.89$, 91.98, -127.48 kJ/mol for the linear, bent, and bridging forms of them, respectively. And the bond lengths between N and O in NO complexes, which becomes longer than NO molecule, indicates that O is easily reduced from Cu-NO. In addition, the Cu-NO complexes using Cu catalyst can be easily measured by infrared or Raman spectroscopy because in the IR and Raman spectra of the NO and Cu-NO complexes the positon and the intensity of bands are definitely different in each vibration mode.

Coordination Polymers Consisting of Unusual Motifs. Synthesis and Properties of Silver(I) and Copper(II) Complexes of Triethanolaminetriisonicotinate

  • Noh, Tae-Hwan;Lee, Jung-Woon;Lee, Young-A;Lee, Ji-Eun;Lee, Shim-Sung;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.29 no.3
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    • pp.562-566
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    • 2008
  • Reaction of AgNO3 with triethanolaminetriisonicotinate (L) produces 1 D coordination polymer of [Ag3(L)2](NO3)3 and the same treatment of Cu(NO3)2 with L gives 1D coordination polymer of [Cu(L)2](NO3)2. The nonrigid triethanolaminetriisonicotinate acts as a m 3-bridged tridentate for [Ag3(L)2](NO3)3 and a m 2-bridged bidentate for [Cu(L)2](NO3)2 to produce unusual motifs. The NO3- anions can be smoothly exchanged by PF6- anions in an aqueous suspension without destruction of the skeletal structure.

Copper(II) Oxyanion Complexes Derived from Sparteine Copper(II) Dinitrate: Synthesis and Characterization of 4- and 5-Coordinate Copper(II) Complexes

  • Lee, Yong-Min;Kim, Yong-Kyu;Jung, Hee-Cheul;Kim, Young-Inn;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.23 no.3
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    • pp.404-412
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    • 2002
  • Nine copper(Ⅱ) oxyanion, and mixed oxyanion complexes that have four- or five-coordinate geometries around copper(Ⅱ) centers were derived from sparteine copper(Ⅱ) dinitrate precursor [Cu($C_{15}$$H_{26}$N2)(NO3)2]. The precursor complex undergoes an anion exchange with various oxyanions, and an interchange reaction with other sparteine copper(Ⅱ) complexes. The [Cu($C_{15}$$H_{26}$N2)(CH3CO2)2] also undergoes "halogen atom abstraction" reaction with CCl4 to produce the mixed anion complex [Cu($C_{15}$$H_{26}$N2)(CH3CO2)Cl]. The whole set of prepared complexes has been used for the comparative electrochemical and spectroscopic studies.

Preparation of Copper Nanoparticles in Cellulose Acetate Polymer and the Reaction Chemistry of Copper Complexes in the Polymer

  • Shim, Il-Wun;Noh, Won-Tae;Kwon, Ji-Woon;Jo, Jung-Young;Kim, Kyung-Soo;Kang, Dong-Hee
    • Bulletin of the Korean Chemical Society
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    • v.23 no.4
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    • pp.563-566
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    • 2002
  • Copper complexes have been directly incorporated into cellulose acetate (CA) and the resulting light blue colored homogeneous films of 5-20 wt.% copper acetate complex concentrations are found to be thermally stable up to 200 $^{\circ}C$. The reaction chem istry of Cu in CA has been investigated by reacting them with small gas molecules such as CO, H2, D2, O2, NO, and olefins in the temperature range of 25-160 $^{\circ}C$, and various Cu-hydride, -carbonyl, -nitrosyl, and olefin species coordinated to Cu sites in CA are characterized by IR and UV/Vis spectroscopic study. The reduction of Cu(II) complexes by reacting with H2 gas at the described conditions results in the formation of Cu2O and copper metal nanoparticles in CA, and their sizes in 30-120 nm range are found to be controlled by adjusting metal complex concentration in CA and/or the reduction reaction conditions. These small copper metal particles show various catalytic reactivity in hydrogenation of olefins and CH3CN; CO oxidation; and NO reduction reactions under relatively mild conditions.

Cupric Complexes Produced from the Reaction of Cupric Nitrate Trihydrate with S-2-Pyridyl Thioates

  • Choi, Young-Nam;So, Hyun-Soo;Lee, Jae-In;Kim, Sung-Gak
    • Bulletin of the Korean Chemical Society
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    • v.7 no.5
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    • pp.385-388
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    • 1986
  • The reaction of cupric nitrate trihydrate with S-2-pyridyl thioates in acetonitrile was studied. The major products were the corresponding carboxylic acids and $[Cu(NO_3)(C_5H_4NS)(C_5H_5NS$)] (Complex A). Sometimes $[Cu(NO_3)(C_5H_4NS)(H_2O$)] was also obtained in addition to Complex A. When Complex A was recrystallized in dimethylsulfoxide, $[Cu(NO_3)(C_5H_4NS)(C_5H_5NS)$ {$(CH_3)_2SO$}$_2]{\cdot}2H_2O$ was crystallized. The structures of these copper complexes and the role of cupric nitrate in the hydrolysis of S-2-pyridyl thioates are discussed.

Structures and Magnetic Properties of Monomeric Copper(II) Bromide Complexes with a Pyridine-Containing Tridentate Schiff Base

  • Kang, Sung Kwon;Yong, Soon Jung;Song, Young-Kwang;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3615-3620
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    • 2013
  • Two novel copper(II) bromide complexes with pyridine containing Schiff base ligands, $Cu(pmed)Br_2$ and $Cu(pmed)Br_2$ where pmed = N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (pmed) and dpmed = N,N-diethyl-N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (dpmed) were synthesized and characterized using X-ray single crystal structure analysis, optical and magnetic susceptibility measurements. Crystal structural analysis of $Cu(pmed)Br_2$ showed that the copper(II) ion has a distorted square-pyramidal geometry with the trigonality index of ${\tau}=0.35$ and two intermolecular hydrogen bonds, which result in the formation of two dimensional networks in the ab plane. On the other hand, $Cu(pmed)Br_2$ displayed a near square-pyramidal geometry with the value of ${\tau}=0.06$. In both compounds, the NNN Schiff base and one Br atom occupy the basal plane, whereas the fifth apical position is occupied by the other Br atom at a greater Cu-Br apical distance. The reported complexes show $g_{\mid}$ > $g_{\perp}$ > 2.0023 with a $d_{x2-y2}$ ground state and a penta-coordinated square pyramidal geometry. Variable temperature magnetic susceptibility measurements showed that the developed copper(II) complexes follow the Curie-Weiss law, that is there are no magnetic interactions between the copper(II) ions since the Cu--Cu distance is too far for magnetic contact.

Chemical Equilibria of Lanthanide {Ln(III)=Pr, Sm, Gd, Dy}-Macrocyclic Complexes with Auxiliary Ligands in $CH_3OH$(Part III); Study of the Coordination of Nitrogen-or Oxygen-Containing Bases ($CH_3OH$ 용매에서 란탄족 원소 {Ln(III)=Pr, Sm, Gd, Dy}-거대고리 착물과 보조리간드 간의 화학평형(제3보); 두자리 리간드(주게원자:N혹은 O)를 중심으로 고찰)

  • Byun, Jong-Chul;Park, Yu-Chul;Han, Chung-Hun
    • Journal of the Korean Chemical Society
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    • v.44 no.2
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    • pp.95-101
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    • 2000
  • Macroacyclic transition metal complexes such as $Cu(H_2L[A]).H_2O$, $Cu(H_2L[B]).H_2O$, CuFe(L[A]($NO_3$).$4H_2O$, CuFe(L[B])($NO_3$).$4H_2O$, [$CuGd(H_2L[A])(NO_3)_2](NO_3).2CH_3OH$, [CuGd($H_2L$[B])($NO_3)_2$]($NO_3).2CH_3OH were prepared from the corresponding hexadentate compartmental ligands, $H_4L[A]$ and $H_4L[B]$, which were obtained by the condensation of 2-hydroxy-3-hydroxymethy1-5-methyIbenzaldehyde(HHNNB) and ethylenediamine or l,3-diaminopropane. Ln-macrocyclic([20]DOTA) complexes,[Ln([20]DOTA)($NO_3)(H_2O)$]($NO_3$)2.$xH_2O${Ln(III)=Pr, Sm, Gd, Dy, which had been synthesized from 2,6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and [Ln([20] DOTA)($NO_3)(CH_3OH)]^{2+}$ was formed The equilibrium constants (k) for the substitution of coordinated $CH_3OH$ in the Ln-[20]DOTA complexes by various bidentate auxiliary ligands, $L_a$(=o-phenylenediamine,1,10-phenanthroline, ethylenediamine,oxalicacid, malonic acid, acethylacetone) were determined by spectroscopic method at $25^{\circ}C$ and 0.1M $NaClO_4$.The pKa of auxiliary ligands is in the order of o-phenylenediamine < 1,10-phenanthroline < ethylene-diamine, oxalic acid < malonic acid < acethylacetone. However, the equilibrium constant(K) has shown thetrend of ethyleneiamine < 1,10-phenanthroline < o-phenylenediamine, acethylacetone < malonic acid < oxalic acid.

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Decomposition Studies of DFP Using Transition Metal Catalysts (전이금속촉매를 사용한 DFP 분해 성능 연구)

  • Kye, Young-Sik;Jeong, Keunhong;Chung, Woo Young
    • Applied Chemistry for Engineering
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    • v.21 no.1
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    • pp.1-5
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    • 2010
  • Cu(II)-organic complexes were synthesized with Lewis base organic ligands including diamine, aminothiol, and dithiol to determine the reactivity for DFP hydrolysis. Results show that the aminothiol catalyst enhances the hydrolysis of DFP in three folds compared to diamine type because aminothiol has higher basicity than diamine. Due to low solubility of Cu(II)(1,2-ethane dithiol)$(NO_3)_2$, it is impossible to compare directly the rates in homogeneous condition. However, the rate of dithol complex is even 1.6 times faster than that of the diamine type. The reactivity of zeolite for DFP hydrolysis is also evaluated. NaY type does not promote the hydrolysis, but RuNaY shows relatively lower reactivity than those of Cu(II)-organic ligands complexes.

Evaluation of Metal-Amino Acid Chelates and Complexes at Various Levels of Copper and Zinc in Weanling Pigs and Broiler Chicks

  • Lee, S.H.;Choi, S.C.;Chae, B.J.;Lee, J.K.;Acda, S.P.
    • Asian-Australasian Journal of Animal Sciences
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    • v.14 no.12
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    • pp.1734-1740
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    • 2001
  • Feeding trials using weanling pigs and broiler chicks were conducted to evaluate the efficacy of different metal-amino acid chelates and complexes at various levels of copper and zinc on the performance and fecal excretions. A total of 200 weanling pigs (Large White ${\times}$ Yorkshire ${\times}$ Duroc, $11.20{\pm}0.81kg$) were randomly assigned to 5 dietary treatments following a randomized complete block design. Each treatment was replicated 4 times with 10 pigs per pen. The dietary treatments were designated as : A-diet containing 170 ppm Cu from $CuSO_4$ and 120 ppm Zn from $ZnSO_4$, B-diet containing 85 ppm Cu from Cu-amino acid chelate (CAC) and 60 ppm Zn from Zn-amino acid chelate (ZAC), C-diet containing 170 ppm Cu from CAC and 120 ppm Zn from ZAC, D-diet containing 85 ppm Cu from Cu-lysine complex (CL) and 60 ppm Zn from Zn-methionine complex (ZM), and E-diet containing 170 ppm Cu from CL and 120 ppm Zn from ZM. On the other trial, 144 of one day old broiler chicks were randomly distributed to 6 dietary treatments following a completely randomized design. Each treatment was replicated 3 times with 8 chicks per replicate. The dietary treatments were as follows: 1-diet with 60 ppm Cu from $CuSO_4$ and 40 ppm Zn from $ZnSO_4$, 2-diet with 120 ppm Cu from $CuSO_4$ and 80 ppm Zn from $ZnSO_4$, 3-diet with 60 ppm Cu from CAC and 40 ppm Zn from ZAC, 4-diet with 120 ppm Cu from CAC and 80 ppm Zn from ZAC, 5-diet with 60 ppm Cu from CL and 40 ppm Zn from ZM, and 6-diet with 120 ppm Cu from CL and 80 ppm Zn from ZM. In Exp. 1 with pigs, there was no difference on average daily gain and average daily feed intake observed among treatments. There was improvement (p<0.05) on the overall feed conversion ratio (FCR) of pigs fed diet containing 120 ppm Zn and 170 ppm Cu from metal-amino acid chelates relative to those fed diet containing inorganic sources of Cu and Zn but equally efficient as those fed diet containing metal-amino acid complexes. Pigs fed diet containing either metal-amino acid chelates or complexes as sources of Cu and Zn had higher (p<0.05) Cu and Zn concentration in serum and lower (p<0.05) in feces than those receiving diet with inorganic sources. In Exp. 2 with broiler chicks, the overall FCR was not different among treatments. Higher (p<0.05) Cu and Zn concentration in serum was obtained from birds fed diet with 60 ppm Cu and 40 ppm Zn from metal-amino acid chelates compared to those fed diet with inorganic sources of Cu and Zn. Also, the feces collected from birds fed diet with either metal-amino acid chelates or complexes contained generally lower Cu and Zn than those birds fed diet with inorganic sources. The higher the dietary level of Cu and Zn the higher the Cu and Zn concentration in the feces. Based on the results, both metal-amino acid chelates and complexes of Cu and Zn at low levels (Zn 60 ppm, Cu 85 ppm for weanling pigs and Zn 40 ppm, Cu 60 ppm for broiler chicks) are not different from that of high levels of inorganic sources in maintaining growth performance and serum concentration. The fecal excretions for Cu and Zn were greatly reduced when organic sources were used.

Structural and Magnetic Properties of Monomeric and Dimeric Copper(II) Complexes with Phenyl-N-[(pyridine-2-yl)methylene]methaneamide

  • Lee, Hong-Woo;Sengottuvelan, Nallathambi;Seo, Hoe-Joo;Choi, Jae-Soo;Kang, Sung-Kwon;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.29 no.9
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    • pp.1711-1716
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    • 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.