• Title/Summary/Keyword: macrocyclic ligand

Search Result 94, Processing Time 0.023 seconds

Synthesis of New Tetraaza Macrocyclic Ligands with Cyclohexane Rings and their Ni(Ⅱ) and Cu(Ⅱ) Complexes

  • Shin-Geol Kang;Jae Keun Kweon;Soo-Kyung Jung
    • Bulletin of the Korean Chemical Society
    • /
    • v.12 no.5
    • /
    • pp.483-487
    • /
    • 1991
  • The tetraaza macrocyclic ligand 3,14-dimethyl-2,6,13,17-tetraazatricyclo $[14,4,0^{1.18} ,0^{7.12}]$docosa-2,12-diene(B), that contains two cyclohexane rings, has been prepared as its dihydroperchlorate salt by the nontemplate condensation of methyl vinyl ketone with 1,2-diaminocyclohexane and perchloric acid. Reduction of B with sodium borohydride produces 3,14-dimethyl-2,6,13,17-tetraazatricyclo$[14,4,0^{1.18},0^{7.12}]$docosane(C). Square planar Ni(Ⅱ) and Cu(Ⅱ) complexes of B and C have been prepared by the reaction of the metal ions and the ligands. Synthesis, characterization, and the properties of the ligands and their metal complexes are reported.

Synthesis and Characterization of 14-Membered Tetraaza Macrocycles with N-Ethyl Groups and their Nickel(Ⅱ) and Copper(Ⅱ) Complexes

  • Kang Shin-Geol;Kweon Jae Keun
    • Bulletin of the Korean Chemical Society
    • /
    • v.13 no.3
    • /
    • pp.256-259
    • /
    • 1992
  • The 14-membered tetraaza macrocyclic ligand 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradeca-4,11-diene(B) can be synthesized as its dihydroperchlorate salt by the one-pot reaction of 2-ethylaminoethylamine, methylvinyl ketone, and perchloric acid in absolute ethanol. The reaction of Ni(II) or Cu(II) ion and the salt yields $[M(B)]^{2+}$ (M = Ni(II) or Cu(II)), which reacts with $NaBH_4$ to produce $[M(D)]^{2+}$ (D = 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradecane). The complexes $[M(L)]^{2+}$ (L = B or D) have planar geometry and contain two ethyl groups at the donor nitrogen atoms of the ligands. The red solids $[Cu(B)](X)_2(X)$ = $ClO_4-$ or $PF_6^-$) react with water molecules of atmospheric moisture to produce the purple solids in which water molecules are coordinated to the metal ion. Synthesis, characterization, and the properties of the new N-ethylated macrocyclic ligands and their Ni(II) and Cu(II) complexes are reported.

Kinetic Study of Macrocyclic Ligand-Metal Ion Complexes (거대고리 리간드와 금속이온과의 착물에 관한 반응속도론적 연구)

  • Moon-Hwan Cho;Jin-Ho Kim;Hyu-Bum Park;Si-Joon Kim
    • Journal of the Korean Chemical Society
    • /
    • v.33 no.4
    • /
    • pp.366-370
    • /
    • 1989
  • A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

  • PDF

Synthesis and Spectroscopic Characterization of Manganese(II), Iron(III) and Cobalt(III) Complexes of Macrocyclic Ligand. Potential of Cobalt(III) Complex in Biological Activity

  • El-Tabl, Abdou S.;Shakdofa, Mohamad M.E.;El-Seidy, Ahmed M.A.
    • Journal of the Korean Chemical Society
    • /
    • v.55 no.6
    • /
    • pp.919-925
    • /
    • 2011
  • A new series of manganese(II), iron(III) and cobalt(III) complexes of 14-membered macrocyclic ligand, (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane-1,8-diamine) have been prepared and characterized by elemental analyses, IR, UV-VIS, $^1H$- and $^{13}C$- NMR spectra, magnetic susceptibilities, conductivities, and ESR measurements. Molar conductance measurements in DMF solution indicate that the complexes are electrolytes. The ESR spectrum for cobalt(III) complex in $CD_3OD+10%D_2O$ after exposure to $^{60}Co-{\gamma}$-rays at 77 K using a 0.2217 M rad $h^{-1}$ vicrad source showed $g_{\perp}$ > $g_{\parallel}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_z2$ orbital with covalent bond character. In this case, the ligand hyperfine tensors are nearly collinear with ${\gamma}$-tensors, so there is no major tendency to bend. Therefore, little extra delocalization via the ring lobe of the $dz^2$ orbital occurs. However, the ESR spectrum in solid state after exposure to $^{60}Co-{\gamma}$-rays at 77 K showed $g_{\parallel}$ > $g_{\perp}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_x2_{-y}2$ ground state as the resulting spectrum contains a large number of randomly oriented molecules provided that, the principle directions of g and A tensors. Manganese (II) complex 2, $[H_{12}LMn]Cl_4.2H_2O$, showed six isotropic lines characteristic to an unpaired electron interacting with a nucleus of spin 5/2, however, iron(III) complex 3, $[H_{12}LFe]Cl_5.H_2O$, showed spectrum of a high spin $^{57}Fe$ (I=1/2), $d^5$ configuration. The geometry of these complexes was supported by elemental analyses, IR, electronic and ESR spectral studies. Complex 1 showed exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

Studies on the Complexes of Lanthanide ion with Multidentate Ligand (I). Determination of Thermodynamic Parameters with Solution Calorimetric Method in Nonaqueous Solvents (란탄족 원소의 여러자리 리간드 착물에 관한 연구 (제 1 보) 물아닌 용액에서 용액열량계에 의한 열역학적 함수결정)

  • Sam-Woo Kang;Won-Hae Koo;Soo-Min Lee;Chang Choo-Hwan;Moo-Yol Seo
    • Journal of the Korean Chemical Society
    • /
    • v.33 no.6
    • /
    • pp.588-595
    • /
    • 1989
  • Log K, ${\Delta}$H and ${\Delta}$S for the complexation of $La^{3+},\;Ce^{3+}$ and $Eu^{3+}$with various multidentate ligand containing crown ether, diaza crown ether and diamine ether have been determined in methanol and acetonitril solutions at $25^{\circ}C$ by solution calorimetric titration method. The greater stability constant of $La^{3+}$-15C5 than those of 18C6 diaza [2.2] in methanol are discussed in terms of the size of metal ion and the ligand cavity and of metal ion solvation. The stabilities of $Ce^{3+}$ and $La^{3+}$ ion complexes with a various multidentate ligand in acetonitril are in the order of (diamine ether)<18C6<15C5$Ce^{3+}$, $La^{3+}$ and $Eu^{3+}$-diaza [2.2] complexes in acetonitril are increased with the following order: $Eu^{3+}$ < $La^{3+}$ < $Ce^{3+}$, that is increasing order of the optimum size and of the charge density of metal ion.

  • PDF

Studies on the Macrocycle-mediated Transport of Divalent Metal Ions in a Supported Liquid Membrane System

  • 조문환;신상철
    • Bulletin of the Korean Chemical Society
    • /
    • v.16 no.1
    • /
    • pp.33-36
    • /
    • 1995
  • Macrocyclic ligands have been studied as cation carriers in a supported liquid membrane system. Cd2+ has been transported using nitrogen substituted macrocycles as carriers and several divalent metal ions (M2+=Zn, Co, Ni, Cu, Pb, Mg, Ca, and Sr) have been transported using DBN3O2, DBN2O2and PolyNtnoen as carriers in a supported liquid membrane system. Competitive Cd2+-M2+ transport studies have also been carried out with the same system. Ligand structure, stability constant, membrane solvent and carrier concentration are also important parameters in the transport of metal ions.

Cyclometalated Platinum(II) Complexes Derived from a Chiral Pyridine Ligand: Synthesis, Structure, and Catalytic Activity

  • Yoon, Myeong-Sik;Ryu, Do-Wook;Kim, Jeong-Ryul;Ramesh, Rengan;Ahn, Kyo-Han
    • Bulletin of the Korean Chemical Society
    • /
    • v.28 no.11
    • /
    • pp.2045-2050
    • /
    • 2007
  • The reactions of mercury(II) chloride with O3S2-donor macrocyclic ligands with (L1) and without (L2) dibenzosubunit afforded respective exo- (1) and endo-coordinated (2) complexes depending on the ring rigidity of the ligands. From the X-ray crystal structures and comparative NMR studies for the complexes 1 and 2, it is confirmed that the resulting species with different coordination modes exist not only in solid state but also in solution state.

Adsorption of Metal Ions on Synthetic Resin with Styrene Hazardous Materials in Water Fire Extinguishing Agent (물 소화약제에서 스타이렌 위험물을 포함한 합성수지에 의한 금속 이온들의 흡착)

  • Lee, Chi-Young;Kim, Joon-Tae
    • Applied Chemistry for Engineering
    • /
    • v.21 no.2
    • /
    • pp.142-147
    • /
    • 2010
  • Cryptand resins have been synthesized from 1-aza-18-crown-6 macrocyclic ligand attached to styrene (2th petroleum in 4th class hazardous materials) divinylbenzene copolymer with crosslinkage of 1%, 2%, 10%, and 18% by substitution reaction. The synthesis of these resins was confirmed by the content of chlorine, element analysis, surface area (BET), and IR-spectroscopy. The effects of pH, time and crosslinkage on adsorption of metal ion from water fire extinguishing agentby synthetic resin adsorbent were investigated. Metal ions showed a great adsorption over pH 3 and adsorption equilibriumof metal ions was about two hours. The adsorption selectivity determined in water was in the increasing order of sodium ($Na^{1+}$) > zinc ($Zn^{2+}$) > chromium ($Cr^{3+}$) ion. The adsorption was in the order of 1%, 2%, 10%, and 18% crosslinkage resin.

Adsorption Characteristic of Rare Earth Metal Ions on 1-Aza-15-Crown-5-Styrene (Hazardous Materials)-DVB Resin (1-Aza-15-Crown-5-Styrene (위험물)-DVB 수지에 의한 희토류 금속 이온들의 흡착 특성)

  • Roh, Gi-Hwan;Kim, Kwan-Chun;Kim, Sun-Hwa;Kim, Joon-Tae
    • Applied Chemistry for Engineering
    • /
    • v.20 no.1
    • /
    • pp.21-27
    • /
    • 2009
  • Resins were synthesized by mixing 1-aza-15-crown-5 macrocyclic ligand attached to styrene (a hazardous material) divinylbenzene (DVB) copolymer with crosslink of 1%, 2%, 5% and 20% by a substitution reaction. The characteristic of these resins was confirmed by the content of chlorine, element analysis, thermogravimetric analysis (TGA), surface area (BET), and IR-spectroscopy. The effects of pH, time, dielectric constant of solvents and crosslink on adsorption of metal ions by the synthetic resin adsorbent were investigated. The metal ion was showed a fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order of uranium ($UO_2^{2+}$) > manganese ($Mn^{2+}$) > praseodymium ($Pr^{3+}$). The adsorption was in the order of 1%, 2%, 5%, and 20% crosslink resin and adsorption of resin decreased in proportion to the order of dielectric constant of solvents.

Adsorption of Uranium (VI) Ion on Synthetic Resin Adsorbent with Styrene Hazardous Materials (Styrene 위험물을 포함한 합성수지 흡착제에 의한 우라늄(VI) 이온의 흡착)

  • Kim, Joon-Tae
    • Applied Chemistry for Engineering
    • /
    • v.20 no.2
    • /
    • pp.165-171
    • /
    • 2009
  • Resins were synthesized by mixing 1-aza-15-crown-5 macrocyclic ligand attached to styrene (2th petroleum in 4th class hazardous materials) and divinylbenzene (DVB) copolymer with crosslinkage of 1%, 2%, 8%, and 16% by substitution reaction. The characteristic of these resins was confirmed by content of chlorine, element analysis, thermogravimetric analysis (TGA), surface area (BET), and IR-spectroscopy. The effects of pH, time, dielectric constant of solvent and crosslinkage on adsorption of metal ion by the synthetic resin adsorbent were investigated. The metal ion showed a fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in an increasing order of uranium $(UO_2^{2+})$ > lead $(Pb^{2+})$ > chromium $(Cr^{3+})$ ion. The adsorption was in the order of 1%, 2%, 8%, and 16% crosslinkage resin and adsorption of resin decreased in proportion to the order of dielectric constant of solvents.