• Title/Summary/Keyword: $NiL^{2+}$

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Chemical Reactivity between Ni(II)-Macrocycle Complex Ions ($NiL_m{^{2+}}$) and $CN^-$ (Ni(II)-거대고리 리간드 착이온 ($NiL_m{^{2+}}$) 과 $CN^-$ 이온간의 반응성)

  • Yu-Chul Park;Jong-Chul Byun
    • Journal of the Korean Chemical Society
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    • v.31 no.4
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    • pp.334-343
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    • 1987
  • The Chemical reactions between $NiL_m{^{2+}}\{$Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}$}\and\ CN^-$ ion were studied by the spectrophotometric method. The equilibrium constants (K_1$) for the 1:1 complex ion, $[NiL_m(CN)]^+\;with\;NiL_m{^{2+}}\;and\;CN^-$ ion were determined in the range of 3 to $25^{\circ}C$. The $K_1\;for\;Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;at\;15^{\circ}C$ was 4.7, 5.3, 6.2, 7.5, 9.4, and 9.8, respectively. The values of $K_1$ decreased with increasing temperature. From the temperature effect on equilibrium constant ($K_1$), thermodynamic parameters $({\Delta}H^{\circ},\;{\Delta}S^{\circ},\;{\Delta}G^{\circ})$ for reaction were evaluated and the reaction of $NiL_m{^{2+}}\;and\;CN^-$ ion was exothermic. $NiL_m{^{2+}\;reacts\;with\;CN^-$ ion to give $Ni(CN)_4{^{2-}}$ ion and macrocyclic ligand $(L_m)$. The kinetics of formation of the $Ni(CN)_4{^{2-}}$ ion of varying the $[CN^-],\;[HCN],\;and\;[OH^-]$ have been investigated at 3∼$25^{\circ}C\;and\;0.5M\;NaClO_4$. Maintaining a constant $[CN^-],\;k_{obs}/[CN^-]^2$ increases linearly with increasing [HCN]. In the presence of large quantities of $[OH^-],\;k_{obs}/[CN^-]^2$ also increases linearly with $[OH^-]$. From the temperature effect on kinetic constant (k_{obs})$, parameter of activation $({\Delta}H^{\neq},\;{\Delta}S^{\neq})$ of reaction of $NiL_m{^{2+}}\;with\;CN^-$ ion were determined. For the $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;series\;{\Delta}H^{\neq}$ gradually decrease as the d-d transition energy, $ν(cm^{-1})$ decrease. And the reaction of the five $NiL_m{^{2+}}\;with\;CN^-$ ion take place by way of equal paths.

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A Study on the Complexation of Nickel(II) Ion with 2-(2-Hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol(Monotris) in Aqueous Solution (수용액 중에서 Ni(II) 이온과 2-(2-Hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol(Monotris)과의 착물형성에 대한 연구)

  • Hong, Kyung-Hee;Shim, Seung-Bo;Oh, Seong-Geun;Chun, Yong-Jin
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.11 no.12
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    • pp.5221-5231
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    • 2010
  • The complex formation from Ni(II) ion and 2-(2-Hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol(Monotris) in aqueous solution at $25^{\circ}C$ and at ionic strength of 0.10M has been studied potentiometrically. In the Monotris(L) comlex $NiL^{2+}$, hydroxyl oxygen atom as well as the amine nitrogen of the ligand are coordinated to the Ni(II) ion.. The complex $NiL^{2+}$ undergoes further dissociation as the pH is increased forming triply deprotonated dinuclear complex $Ni_2L_2H_{-3}^+$.

Synthesis and Characterization of Ni(Ⅱ) Complexes with Aminophosphine, Ni(L)X$_2$ and [Ni(L)$_2$]Cl$_2$ (L = L$_1$, L$_2$ ; X = Cl$^-$, Br$^-$, I$^-$) (Aminophosphine류 리간드가 배위된 Ni(Ⅱ) 착물, Ni(L)X$_2$ 및 [Ni(L)$_2$]Cl$_2$ (L = L$_1$, L$_2$ ; X = Cl$^-$, Br$^-$, I$^-$)의 합성과 성질)

  • Jeong, Maeng Jun;Park, Sang Gyu;Jeong, Min Ho;Kim, Bong Gon;Do, Myeong Gi
    • Journal of the Korean Chemical Society
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    • v.38 no.4
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    • pp.288-294
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    • 1994
  • Several new nickel(II) complexes, [Ni(L)X$_2$ and [Ni(L)$_2$]Cl$_2$ (L = L$_1$, L$_2$ ; X = Cl$^-$, Br$^-$, I$^-$) have been synthesized by reacting NiX$_2$ or NiX$_2$, 6H$_2$O with aminophosphines(L) wherein L is 1,2-bis{(diphenylphosphino)amino}propane(L$_1$) or 1,2-bis{(diphenylphosphino)amino}ethane(L$_2$). These complexes are characterized by the optical spectroscopic methods (UV/Vis, CD, IR, $^1$H-NMR, and $^{31}$P-NMR) together with conductometer and elemental analysis. The complex with I$^-$ is tetrahedral, where the complexes with Cl$^-$ or Br$^-$ are square planar. The complexes, [Ni(L)X$_2$](X = Cl$^-$, Br$^-$) become tetrahedral, as they react with methyl iodide. The Ni(L)X$_2$ complexes underwent solvolysis with a various organic solvents such is EtOH, DMSO, THF and DMF.

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Synthesis and Characterization of New Polyaza Non-macrocyclic and Macrocyclic Nickel(II) Complexes Containing One 1,3-Diazacyclohexane Ring

  • Lee, Yun-Taek;Jang, Bo Woo;Kang, Shin-Geol
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2125-2130
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    • 2013
  • A new nickel(II) complex $[NiL^1]^{2+}$ ($L^1$ = 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl-1,3-diazacyclohexane) containing one 1,3-diazacyclohexane ring has been prepared selectively by the metal-template condensation of formaldehyde with N-(2-aminoethyl)-1,3-propanediamine and ethylenediamine at room temperature. The complex reacts with nitroethane and formaldehyde to yield the pentaaza macrocyclic complex $[NiL^2]^{2+}$ ($L^2$ = 8-methyl-8-nitro-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one C-$NO_2$ pendant arm. The reduction of $[NiL^2]^{2+}$ by using Zn/HCl produces $[NiL^3(H_2O)]^{2+}$ ($L^3$ = 8-amino-8-methyl-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one coordinated C-$NH_2$ pendant arm that is readily protonated in acid solutions. The hexaaza macrocyclic complex $[NiL^4]^{2+}$ ($L^4$ = 8-phenylmethyl-8-nitro-1,3,6,8,10,13-hexaazabicyclo[13.3.1]heptadecane) bearing one N-$CH_2C_6H_5$ pendant arm has also been prepared by the reaction of $[NiL^1]^{2+}$ with benzylamine and formaldehyde. The nickel(II) complexes of $L^1$, $L^2$, and $L^4$ have square-planar coordination geometry in the solid states and in nitromethane. However, they exist as equilibrium mixtures of the square-planar $[NiL]^{2+}$ (L = $L^1$, $L^2$, or $L^4$) and octahedral $[NiL(S)_2]^{2+}$ species in various coordinating solvents (S); the proportion of the octahedral species $[NiL(S)_2]^{2+}$ is strongly influenced by the ligand structure and the nature of the solvent. Synthesis, spectra, and chemical properties of the nickel(II) complexes of $L^1-L^4$ are described.

Synthesis of a Di-N-cyanoethylated Tetraaza Macrocycle Containing Eight C-Methyl Groups and Its Nickel(II) Complex: Effects of the Methyl Groups on Their Properties

  • Kang, Shin-Geol;Ryu, Ki-Seok;Kim, Jin-Kwon
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.81-85
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    • 2002
  • A new di-N-cyanoethylated 14-membered tetraaza macrocycle 1,8-bis(2-cyanoethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^2)$ and its nickel(II) complex $[NiL^2(OAc)]^+$ have been prepared. The square-planar complex $[NiL^2](C IO_4)_2$ can be prepared by addition of $HClO_4$ to a hot aqueous solution of $[NiL^2(OAc)]^+$ The Ni-N (tertiary amino group) bond distances $(2.008{\AA})$ of $[NiL^2](C IO_4)_2$ are relatively long, and the complex exhibits a d-d transition band at unusually long wavelength (ca. 515 nm). The complex $[NiL^2](C IO_4)_2$ rapidly reacts with acetate ion or ethylenediamine (en) to produce $[NiL^2(OAc)]^+$ or [Ni(en)_3]^{2+}$, respectively, and is readily decomposed in NaOH (0.01 M) solution. The chemical properties of $[NiL^2]^{2+}$ as well as its synthetic procedure are quite different from those for other related 14-membered tetraaza macrocyclic complexes. Effects of the N-cyanoethyl and C-methyl groups on the properties of $L^2$.

Bioassessment of Nanoparticle Toxicity based on Seed Germination and Germination Index of Various Seeds (다양한 씨앗의 발아 및 발아지수에 근거한 나노입자 생물학적 독성평가)

  • Gu, Bon Woo;Lee, Min Kyeung;Shi, Yu Tao;Kong, In Chul
    • Clean Technology
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    • v.21 no.1
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    • pp.39-44
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    • 2015
  • This study investigated the effects of six metal oxide nanoparticles (NPs: CuO, NiO, TiO2, Fe2O3, Co3O4, ZnO) on seed germination and germination index (G.I) for five types of seeds: Brassica napus L., Malva verticillata L., Brassica olercea L., Brassica campestris L., Daucus carota L. NPs of CuO, ZnO, NiO show significant toxicity impacts on seed activities [CuO (6-27 mg/L), ZnO (16-86 mg/L), NiO (48-112 mg/L)], while no significant effects were observed at > 1000 mg/L of TiO2, Fe2O3, Co3O4. Tested five types of seed showed different sensitivities on seed germination and root activity, especially on NPs of CuO, ZnO, NiO. Malva verticillata L. seed was highly sensitive to toxic metal oxide NPs and showed following EC50s : CuO 5.5 mg/L, ZnO 16.4 mg/L, NiO 53.4 mg/L. Mostly following order of toxicity was observed, CuO > ZnO > NiO > Fe2O3 ≈ Co3O4 ≈ TiO2, where slightly different toxicity order was observed for carrot, showing CuO > NiO ≈ ZnO > Fe2O3 ≈ Co3O4 ≈ TiO2.

A Study on the Precipitation Behavior of $L2_1$-type $Ni_2AlTi$ Phase in B2-Ordered NiAl System (B2-규칙 NiAl계에 $L2_1$$Ni_2AlTi$상의 석출거동에 관한 연구)

  • Han, Chang-Suk
    • Journal of the Korean Society for Heat Treatment
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    • v.20 no.4
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    • pp.187-194
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    • 2007
  • A transmission electron microscope (TEM) investigation has been performed on the precipitation of $L2_1$-type $Ni_2AlTi$ phase in B2-ordered NiAl system. The hardness after solution treatment is high in NiAl-Ti alloys suggesting the large contribution of solid solution strengthening in this alloy system. However, the amount of age hardening is not large as compared to the large microstructural variations during aging. At the beginning of aging, the $L2_1$-type $Ni_2AlTi$ precipitates keep a lattice coherency with the NiAl matrix. By longer periods of aging $Ni_2AlTi$ precipitates lose their coherency and change their morphology to the globular ones surrounded by misfit dislocations. Misfit dislocations, which are observed on {100} planes of H-precipitates have the Burgers vector of a <100> with a pure edge type. The lattice misfits of NiAl-$Ni_2AlTi$ system is estimated from the spacings of misfit dislocations to be 1.1% at 1273 K. The lattice misfits decrease with increasing aging temperature in this system.

Optical Absorption and Polarogram of Macrocyclic Nickel (II) Complexes in Polar Solvents (극성용매에서 거대고리 Ni (II) 착물의 광흡수와 폴라로그램)

  • Park Yuj-Chul;Jong-Chul Byun
    • Journal of the Korean Chemical Society
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    • v.31 no.2
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    • pp.168-177
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    • 1987
  • The equilibria of chemical reaction between $\alpha$-Ni(rac-[14]-decane)$^{2+}$ and polar solvents(L; ANT, MFA, DMSO, DMF, and DMA) have been investigated by the spectrophotometric method at $25^{\circ}C$. (The equilibrium constants($K_1$) of) the first step in ANT, MFA, DMSO, DMF, and DMA were 31.0, 27.5, 21.3 15.9, and 6.4, respectively. The smallness of equilibrium constants ($K_2$) of the second step compared with $K_1$, was observed. $\alpha$-Ni(rac-[14]-dacane)$^{2+}$ + L $\leftrightharpoons$ [$\alpha$-Ni(rac-[14]-decane){\cdot}L]$^{2+}$ : $K_1$.[$\alpha$-Ni(rac-[14]-decane){\cdot}L)$^{2+}$+ L $\leftrightharpoons$ [$\alpha$-Ni(rac-[14]-decane){\cdot}$L_2$)$^{2+}$ :$K_2$. The relationship between d-d absorption energy and half-wave potential of complex ions at ACT was considered. Macrocyclic ligands increasing d-d transition energy caused half-wave potentials of Ni(II)-macrocycle to be shifted more positively. The half-wave potentials for Ni(rac-1[14]7-diene)$^{2+}$, Ni(meso-1[14]7-diene)$^{2+}$, Ni(1[14]4-diene)$^{2+}$, $\alpha$-Ni(rac-[14]-decane)$^{2+}$, ${\beta}-Ni(rac-[14]-decane)$^{2+}$, and Ni(meso-[14]-decane)$^{2+}$ reductions were -1.419, -1.431, -1.450, -1.473, and -1.480 (V vs. SCE), respectively. The d-d transition energies ($\nu_{max},\;cm^{-1}$) of the Ni(meso-[14]-decane)$^{2+}$ isomer were discussed with the dielectric constant (${\varepsilon}/{\varepsilon}_0$) of the various solvents, $\nu_{max}(cm^{-1})$ increased with increasing ${\varepsilon}/{\varepsilon}_0$.

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Distribution Behavior of Ni between CaO-SiO2-Al2O3-MgO Slag and Cu-Ni Alloy (CaO-SiO2-Al2O3-MgO 슬래그와 Cu-Ni합금 사이의 Ni 분배거동)

  • Han, Bo-Ram;Sohn, Ho-Sang
    • Resources Recycling
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    • v.24 no.1
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    • pp.35-42
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    • 2015
  • To obtain the fundamental information on the dissolution of nickel into the slag in the pyrometallurgical processes for treatment of wasted PCB, the distribution ratios of nickel between CaO-$SiO_2-Al_2O_3$-MgO slag and copper-5 wt%Ni alloy were measured at 1623 K to 1823 K under a controlled $CO_2$-CO atmosphere. The distribution ratio of Ni increased linearly with increasing oxygen partial pressure. Therefore, the dissolution reaction of nickel into the slags could be described by the following equation; $$Ni(l)_{metal}+\frac{1}{2}O_2(g)NiO(l)_{slag}$$ The distribution ratio of Ni increased linearly with increasing content of basic oxides(CaO and MgO) in slag. However, the distribution ratio of Ni decreased linearly with increasing temperature. From these results, the empirical equation of distribution ratio of Ni was obtained by the following equation from the analysis of experimental conditions by multiple regression. $${\log}L_{Ni}=0.4000{\log}P_{O2}-5.1{\times}10^{-4}T+0.3375\(\frac{X_{CaO}+X_{MgO}}{X_{SiO2}}\)$$

A Study on the Precipitation Behavior of $L2_1$-type Precipitates in B2-NiAl (B2형 NiAl에 석출한 $L2_1$형 석출상의 석출거동에 관한 연구)

  • Han, Chang-Suk;Han, Seung-Oh;Lee, Ju-Hee
    • Journal of the Korean Society for Heat Treatment
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    • v.22 no.6
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    • pp.345-353
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    • 2009
  • The precipitates of $L2_1$-type $Ni_2AlHf$ phase in B2-ordered NiAl system has been observed by using transmission electron microscope (TEM). The hardness of as-quenched NiAl-Hf alloys is high due to the larger strengthening. However, age hardening of this alloy is not main effect to increase hardness compared to the large microstructural variations during aging. At the beginning of aging, the $L2_1$-type $Ni_2AlHf$ precipitates keep a lattice coherency with the NiAl matrix. The orientation relationship between the $Ni_2 AlHf$ precipitate and the NiAl matrix is <100>$_{Ni2AlHf}$//<100>$_{NiAl}$, {001}$_{Ni2AlHf}$//{001}$_{NiAl}$. By aging treatment for long time $Ni_2AlHf$ precipitates lost their coherency and change their morphology to the spherical ones surrounded by misfit dislocations. The orientation relationship between the NiAl matrix and the $Ni_2AlHf$ precipitates, however, has been kept even after longer aging time. The lattice misfit between the $Ni_2AlHf$ precipitate and the NiAl matrix has been calculated by the selected electron diffraction patterns, and the spacings of misfit dislocations is about 4.5% at 1173 K.