• Title/Summary/Keyword: Macrocyclic complex

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Structure and Properties of a Nonheme Pentacoordinate Iron(II) Complex with a Macrocyclic Triazapyridinophane Ligand

  • You, Minyoung;Seo, Mi Sook;Kim, Kwan Mook;Nam, Wonwoo;Kim, Jinheung
    • Bulletin of the Korean Chemical Society
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    • v.27 no.8
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    • pp.1140-1144
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    • 2006
  • A macrocyclic ligand, N,N',N'-tribenzyl-2,11,20-triaza[3,3,3](2,6)pyridinophane (BAPP), was used to prepare an iron(II) complex as a nonheme model complex, $[(BAPP)Fe]^{+2}$ (1). X-ray crystallography of a colorless crystal of 1 revealed that BAPP acted as a pentadentate ligand due to geometrical strain for the formation of a six-coordinate iron(II) complex by BAPP. As a result, the iron center revealed a significantly distorted square pyramidal geometry similar to that found in the active site of taurine dioxygenase (tauD). In the reaction of 1 with PhIO, no intermediate was observed in the UV-visible region of spectrometer at low temperatures. Catalytic oxidations of triphenyl phosphine with PhIO at ${-40^{\circ}C}$ revealed that 1 was able to convert triphenyl phosphine to triphenyl phosphine oxide.23; SSOCHKThioanisole was also oxidized to the corresponding methylphenyl sulfoxide under the same conditions.

The Stability Constant of 1, 7, 10, 16-Tetraoxa-4, 13-Diazacyclooctadecane-Uranium (Ⅵ) Complex in Aqueous Solution

  • Suh, Moo-Yul;Eom, Tae-Yoon;Kim, Si-Joong
    • Bulletin of the Korean Chemical Society
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    • v.4 no.5
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    • pp.231-234
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    • 1983
  • The stability constant for the complex of $UO_2^{2+}$ with a macrocyclic aminoether ligand, 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane, has determined in aqueous solution. The conductivity and pH metric measurements suggest that the ligand forms a stable 1:1 complex with $UO_2^{2+}$ ion, and the complex is an ionic form, $UO_2L^{2+}$, in aqueous solution. The fact that the ligand does not form a complex with lanthanides, such as $Ce^{3+}$, $Sm^{3+}$, and $Nd^{3+}$ ions, in aqueous solution suggests a possibility of separation of the lanthanide elements from uranium matrix using the macrocyclic aminoether ligand.

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

  • Kim, Gilhoon;Won, Hoshik
    • Journal of the Korean Magnetic Resonance Society
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    • v.18 no.2
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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.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part II); Synthesis and Characterization of Cr(III)-Citrato Macrocyclic Complex

  • Byun, Jong-Chul;Park, Yu-Chul;Youn, Jeung-Su;Han, Chung-Hun;Lee, Nam-Ho
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.634-640
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    • 2005
  • The reaction of cis-[Cr([14]-decane)(OH$_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = citrate(cit)} leads to a new dimeric complex cis-[{Cr([14]-decane)($\mu$-cit)}$_2](ClO_4)_2$. This binuclear complex has been structurally characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ reveals that each chromium has a distorted octahedral coordination environment and citrato ligands are monodentate to the two chromium atoms via the carboxyl groups. For dimeric complex the bridging geometry is as follows: Cr$\ldots$Cr = 7.361 $\AA$; Cr-O(average) = 1.958 (8) $\AA$; Cr-N range = 2.108 (9)-2.147(9) $\AA$; N(1)-Cr-N(3) (equatorial position) = 98.0(4)$^{\circ}$; N(2)-Cr-N(4) (axial position) = 166.4(4)$^{\circ}$; O(1)-Cr-N(2) = 98.1(4)$^{\circ}$; O(3)-Cr-N(4) = 96.6(3)$^{\circ}$; O(1)-Cr-O(3) = 90.4$^{\circ}$. The FAB mass spectrum of the dimeric complex displays peak due to the molecular ions cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ at m/z 1053.

Adsorption of Macrocyclic Cobalt Complex on a Glassy Carbon Electrode for the Electrocatalytic Reduction of $O_2$

  • 강찬
    • Bulletin of the Korean Chemical Society
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    • v.19 no.7
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    • pp.754-760
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    • 1998
  • It was found that the adsorption of a cobalt(III) complex with a macrocyclic ligand, C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (hmc), was induced on a glassy carbon electrode by heavily oxidizing the electrode surface. Adsorption properties are discussed. The glassy carbon electrode with the adsorbed complex was employed to see the catalytic activities for the electro-reduction of O2. In the presence of oxygen, reduction of (hmc)Co3+ showed two cathodic waves in cyclic voltammetry. Compared to the edge plane graphite electrode at which two cathodic waves were also observed in a previous study, catalytic reduction of O2 occurred in the potential region of the first wave while it happened in the second wave region with the other electrode. A rotating disk electrode after the same treatment was employed to study the mechanism of the O2 reduction and two-electron reduction of O2 was observed. The difference from the previous results was explained by the different reactivity of the (hmc)CoOOH2+ intermediate, which is produced after the two electron reduction of (hmc)Co3+ in the presence of O2.