• 제목/요약/키워드: Ni(II)-Macrocyclic Complex

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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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    • 제34권7호
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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.

Spectroscopic characterization of N,N'-bis(salicylidene)pentane-1,3-diamine nickel(II) complex

  • Kim, Gilhoon;Won, Hoshik
    • 한국자기공명학회논문지
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    • 제18권2호
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    • pp.74-81
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    • 2014
  • The $N_2O_2$ tetradentate Schiff base ligand, N,N'-bis(salicylidene)pentane-1,3-diamine (Salpn), coupled with 1:2 concentration ratio of 1,3-diaminopentane and salicylaldehyde was used to produce a series of macrocyclic Nikel(II) complexes. In the metal complexation, it was observed that Salpn macrocyclic ligand can adopt more than a metal ion giving an unique multinuclear metal complexes including Ni(II)Salpn and $Ni(II)_3(Salpn)_2$. Characteristic IR ${\upsilon}(M-O)$ peaks for Ni(II)Salpn and $Ni(II)_3(Salpn)_2$ were observed to be $1028cm^{-1}$ and $1024cm^{-1}$, respectively. Characteristic UV-Vis absorption ${\lambda}_{max}$ peaks for $Ni(II)_3(Salpn)_2$ were observed to be 241nm and 401 nm. Structural characterization of $Ni(II)_3(Salpn)_2$ by NMR exhibits that the salicylidene ring moiety has two different resonance signals originated from the magnetically asymmetric diligand and trinuclear bis complex. Complete NMR signal assignments and characterizations elucidating structural features of $Ni(II)_3(Salpn)_2$ were described in detail.

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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    • 제23권1호
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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 $L^2$.

Synthesis and Characterization of Dinuclear Ni(II) Complexes with Tetraazadiphenol Macrocycle Bearing Cyclohexanes

  • Kim, Ki-Ju;Jung, Duk-Sang;Kim, Duk-Soo;Choi, Chi-Kyu;Park, Ki-Min;Byun, Jong-Chul
    • Bulletin of the Korean Chemical Society
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    • 제27권11호
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    • pp.1747-1751
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    • 2006
  • The dinuclear tetraazadiphenol macrocyclic nickel(II) complexes [$Ni_2$([20]-DCHDC)]$Cl_2$ (I), [$Ni_2$([20]-DCHDC)]$(ClO_4)_2{\cdot}2CH_3CN $ (II(b)) and [$Ni_2$([20]-DCHDC)$(NCS)_2$] (III) {$H_2$[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,$0^{4,9}$,$1^{12,16}$,$0^{19,24}$]ditriacontane-2,10,12,14,16(32),17,27(31), 28,30-decane-31,32-diol} have been synthesized by self-assembly and characterized by elemental analyses, conductances, FT-IR and FAB-MS spectra, and single crystal X-ray diffraction. The crystal structure of II(b) is determined. It crystallizes in the monoclinic space group P2(1)/c. The coordination geometries around Ni(II) ions in I and II(b) are identical and square planes. In complex III each Ni(II) ion is coordinated to $N_2O_2$ plane from the macrocycle and N atoms of NCS- ions occupying the axial positions, forming a square pyramidal geometry. The nonbonded Ni…Ni intermetallic separation in the complex II(b) is 2.8078(10) $\AA$. The FAB mass spectra of I, II and III display major fragments at m/z 635.1, 699.4 and 662.4 corresponding to [$Ni_2$([20]-DCHDC)(Cl + 2H)]$^+$, [$Ni_2$([20]-DCHDC)$(ClO_4\;+\;2H)]^+$ and [$Ni_2$([20]-DCHDC)(NCS) + 6H]$^+$, respectively.

Ag(Ⅰ) 이온 선택성을 갖는 거대고리 리간드: 벤질 치환기를 갖는 질소-산소 주개 거대고리 리간드의 착물 형성과 액체막 이동 현상 (Ag(Ⅰ) Ion Selective Macrocyclic Ligands: The Complexation and Liquid Membrane Transport Phenomena of Benzylated Nitrogen-Oxygen Donor Macrocyclic Ligands)

  • 김정;안태호;이명노;조문환;김시중
    • 대한화학회지
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    • 제43권2호
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    • pp.167-171
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    • 1999
  • 벤질 치환기를 포함하는 질소-산소 혼합 주개 거대고리 리간드와 Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II) 그리고 Ag(I)와의 상호작용에 관한 연구를 수행하였다. 95% 메탄올 용액에서 각 착물의 안정도 상수를 전위차 적정법을 통해 결정하였으며 또한 이들 거대고리 리간드를 포함하는 액체막을 통하여 금속 이온의 이동을 조사하였다. 그 결과 Cu(II)와 Ag(I) 이온의 경우만 사용한 두 리간드와 안정한 착물을 형성하는 것으로 조사되었으며 액체막 이동 실험에서는 Ag(I) 이온의 선택적 이동이 일어남을 확인하였다.

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니켈(II)-거대고리 착물과 폴리 우레탄으로 변성한 이중 전극에서 에피네피린의 전기화학적 정량 (Electrochemical Determination of Epinephrine Using Doubly Modified Electrodes with Ni(II)-Macrocyclic Complex and Polyuretane)

  • ;조형화;권수경;이상학;배준웅
    • 전기화학회지
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    • 제10권3호
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    • pp.190-195
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    • 2007
  • 본 연구는 뇨 속에 있는 에피네피린을 선택적으로 정량하기 위한 새로운 전기화학적 센서를 제작하고 그 특성을 연구한 것이다. 전극의 제작은 유리질 탄소전극에 촉매능이 있는 니켈(II)거대고리 착물을 전착시킨 후, 그 위에 생체적합성이 좋으며 음의 하전을 띤 polyuretane benzyl L-glutamate(PUBLG)로 막을 입힌 이중 폴리머 전극이다. 이 전극은 뇨 속에 있는 많은 방해물질에 대하여 좋은 선택성을 보였으며, 우수한 장기 안정성을 보였다. 최적 실험조건하에서 이 전극을 이용한 에피네피린의 정량범위는 $8.0\;{\times}\;10^{-7}\;M$에서 $2.0\;{\times}\;10^{-4}\;M$이고, 검출한계는 $1.0\;{\times}\;10^{-7}\;M$이다. 완충용액으로 5 배 희석한 뇨 시료에서 에피네피린의 회수율은 6 회 측정에서 $101.5({\pm}3.2)%$ 이었다.

Synthesis and Characterization of New Mono-N-functionalized Tetraaza Macrocyclic Nickel(II) and Copper(II) Complexes

  • Kim, Hyun-Ja;Kang, Shin-Geol
    • Bulletin of the Korean Chemical Society
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    • 제32권8호
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    • pp.2565-2570
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    • 2011
  • The reaction of bromoacetonitrile with 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{10}$) containing a N-$CH_2$-N linkage produces 17-cyanomethyl-3,14-dimethyl-2,6,13,17-tetraazatetracyclo-[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{11}$). The mono-N-functionalized macrocyclic complexes $[ML^2]^{2+}$ (M = Ni(II) or Cu(II); $L^2$ = 2-cyanomethyl-5,16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^{7.12}$]docosane) can be prepared by the reaction of $L^{11}$ with nickel(II) or copper(II) ion in acetonitrile. The N-$CH_2CN$ group attached to $[ML^2]^{2+}$ readily reacts with water or methanol to yield the corresponding complexes of $HL^3$ bearing one N-$CH_2CONH_2$ pendant arm or $L^4$ bearing one $N-CH_2C(=NH)OCH_3$ group. The $N-CH_2CONH_2$ or $N-CH_2C(=NH)OCH_3$ group of each complex is coordinated to the central metal ion. Both $[NiL^4(H_2O)]^{2+}$ and $[CuL^4]^{2+}$ are quite stable in acidic aqueous solutions, but undergo hydrolysis to yield $[Ni(HL^3)(H_2O)]^{2+}$ or $[Cu(HL^3)]^{2+}$ in basic aqueous solutions. In contrast to $[Cu(HL^3)]^{2+}$, $[Ni(HL^3) (H_2O)]^{2+}$ is readily deprotonated to form $[NiL^3 (H_2O)]^+$ ($L^3$ = a deprotonated form of $HL^3$) in basic aqueous solutions.

Synthesis and Characterization of Nickel(II) Tetraaza Macrocyclic Complex with 1,1-Cyclohexanediacetate Ligand

  • Lim, In-Taek;Kim, Chong-Hyeak;Choi, Ki-Young
    • 대한화학회지
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    • 제62권6호
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    • pp.427-432
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    • 2018
  • The reaction of [$[Ni(L)]Cl_2{\cdot}2H_2O$ (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[$14,4,0^{1.18},0^{7.12}$]docosane) with 1,1-cyclohexanediacetic acid ($H_2cda$) yields mononuclear nickel(II) complex, [$Ni(L)(Hcda^-)_2$] (1). This complex has been characterized by X-ray crystallography, electronic absorption, cyclic voltammetry and thermogravimetric analyzer. The crystal structure of 1 exhibits a distorted octahedral geometry with four nitrogen atoms of the macrocycle and two 1,1-cyclohexanediacetate ligands. It crystallizes in the triclinic system P-1 with a = 11.3918(7), b = 12.6196(8), $c=12.8700(8){\AA}$, $V=1579.9(2){\AA}^3$, Z = 2. Electronic spectrum of 1 also reveals a high-spin octahedral environment. Cyclic voltammetry of 1 undergoes one wave of a one-electron transfer corresponding to $Ni^{II}/Ni^{III}$ process. TGA curve for 1 shows three-step weight loss. The electronic spectra, electrochemical and TGA behavior of the complex are significantly affected by the nature of the axial $Hcda^-$ ligand.