• 제목/요약/키워드: Schiff base complex

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DMSO용액에서 네자리 Schiff Base Cobalt(II) 착물들의 산소 첨가 생성물에 대한 전기화학적 성질에 관한 연구 (제 1 보) (Studies on The Electrochemical Properties of Oxygen adducts Tetradentate Schiff Base Cobalt(II) Complexes in DMSO (I))

  • 조기형;정진순;함희석;서성섭
    • 대한화학회지
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    • 제31권6호
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    • pp.542-554
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    • 1987
  • 네자리 schiff base cobalt(II) 착물로서 Co(SED), Co(SND) and Co(SOPD)들을 합성하여 이들 착물들의 DMSO 용액에서 산소를 가하여 산소첨가 생성착물로 $[Co(SED)(DMSO)]_2O_2,\;[Co(SND)(DMSO)]_2O_2$$[Co(SOPD)(DMSO)]_2O_2$들을 합성하였다. 이들의 원소분석과 Cobalt정량, IR-Spectra, T.G.A. 및 자화율을 측정하여 산소:cobalt(II) 착물의 결합비가 1:2이고 네자리 schiff base cobalt(II)와 DMSO 및 산소가 6배위 결합으로 주어짐을 알았으며 Co(SED), Co(SND) 및 Co(SOPD) 착물들의 0.1M TEAP-DMSO용액에서 순환전압-전류법에 의한 산화 환원 과정이 Co(SED) 및 Co(SOPD)는 Co(II) / Co(III)와 Co(II) / Co(I) 과정이 가역적으로 일어나고 Co(SND)는 Co(II) / Co(III)과정은 가역적이지만 Co(II) / Co(I) 과정은 비가역적이다. 또한 산소 첨가 생성물의 착물들은 0.1M TEAP-DMSO 용액에서 산소결합의 환원과정이 $E_{pc}$ = -0.80~-0.89V에서 일어나고 이에 Couple인 산화과정은 $E_{pa}$ = -0.70~-0.76V에서 준가역적으로 일어남을 알았다.

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세자리 Schiff Base 리간드의 몰리브덴 착물에 관하여 (제1보) (Studies on the Molybdenum Complexes with Tridentate Schiff Base Ligand (I))

  • 조기형
    • 대한화학회지
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    • 제17권3호
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    • pp.169-173
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    • 1973
  • 세자리 schiff base리간드로서 salicylidene amino-o-hydroxy benzene 은 salicylaldehyde와 o-amino phenol로서 합성하였으며 이 세자리 schiff base 리간드와 Mo(VI), Mo(V), Mo(IV) 및 Mo(III) 의 과산화상태의 몰리브덴 착물들의 반응으로 새로운 착물[Mo O$_2(H_2O)\;(C_{13}H_9O_2N)]$, [MoO Cl(H$_2O)(C_13H_9O_2N)]$, $[Mo(SCN)_2(H_2O)(C_{13}H_9O2_N)]$$[Mo(H_2O)_2 (C_{13}H_9O_2N)]_2O$들을 얻었다. 이들 착물에서 Mo(VI), Mo(V) 및 Mo(IV)착물들은 리간드와 몰리브덴의 mole비가 1:1인 착물로서 몰리브덴 이온은 6배위 팔면체로서 주어지나 Mo(III) 착물은 Mo-O-Mo의 산소 bridge bond를 갖는 poly nuclear 착물로서 mole비 1:1인 착물로 주어짐을 원소분석치와 자외선흡광도 및 적외선 spectra의 고찰로서 알아보았다.

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Structure and Heme-Independent Peroxidase Activity of a Fully-Coordinated Mononuclear Mn(II) Complex with a Schiff-Base Tripodal Ligand Containing Three Imidazole Groups

  • Sarkar, Shuranjan;Moon, Do-Hyun;Lah, Myoung-Soo;Lee, Hong-In
    • Bulletin of the Korean Chemical Society
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    • 제31권11호
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    • pp.3173-3179
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    • 2010
  • New complex $[Mn(II)H_{1.5}L]_2[Mn(II)H_3L]_2(ClO_4)_5{\cdot}3H_2O$ (1), where $H_3L$ is tris {2-(4-imidazolyl)methyliminoethyl} amine (imtren), has been prepared by reacting manganese(II) perchlorate hexahydrate with the imtren ligand in methanol. X-ray crystallographic study revealed that the imtren ligand hexadentately binds to Mn(II) ion through the three Schiff-base imine N atoms and three imidazole N atoms with a distorted octahedral geometry, and the apical tertiary amine N atom of the ligand pseudo-coordinates to Mn(II), forming overall a pseudo-seven coordination environment. The hydrogen-bonds between imidazole and imidazolate of $[Mn(II)H_{1.5}L]^{0.5+}$ complex ions are extended to build a 2D puckered network with trigonal voids. $[Mn(II)H_3L]^{2+}$ complex ions constitutes another extended 2D puckered layer without hydrogen bonds. Two layers are wedged each other to constitute overall stack of the crystal. Peroxidase activity of complex 1 was examined by observing the oxidation of 2,2'-azinobis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) with hydrogen peroxide in the presence of complex 1. Generation of $ABTS^{+{\cdot}}$ was observed by UV-vis and EPR spectroscopies, indicating that the complex 1, a fully-coordinated mononuclear Mn(II) complex with nitrogen-only ligand, has a heme-independent peroxidase activity.

A New Adamantane-like Tetranuclear Manganese(III) Complex Based on Flexible Schiff-base Ligand: Synthesis, Crystal Structure and Magnetic Property

  • Zhang, Ran;Ni, Zhong-Hai;Zhang, Li-Fang;Kou, Hui-Zhong
    • Bulletin of the Korean Chemical Society
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    • 제35권7호
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    • pp.1965-1969
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    • 2014
  • A new tetranuclear Mn(III) complex $[Mn^{III}{_4}(sae)_4({\mu}_3-O)({\mu}_{1,1}-N_3)(OH)(H_2O)_2]{\cdot}H_2O$ (1) ($H_2sae$ = 2-salicylideneamino-1-ethanol) has been synthesized by the reaction of $MnCl_2{\cdot}4H_2O$, $H_2sae$ and sodium azide in the mixed solvent of methanol, acetonitrile and water. The X-ray diffraction analysis shows that the four Mn(III) ions in complex 1 have a unique adamantine arrangement, whereas the coordination environment of each Mn(III) ions is different. Magnetic studies indicate that complex 1 manifests antiferromagnetic behaviors. The magnetic susceptibilities of complex 1 have been fitted by two magnetic models based on the suitable analysis of its magnetic structural topology.

A Theoretical Study on the Alkylation of the Ambident Enolate from a Methyl Glycinate Schiff Base

  • Nahm, Kee-Pyung;Lee, Seung-Min
    • Bulletin of the Korean Chemical Society
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    • 제33권8호
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    • pp.2711-2718
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    • 2012
  • The alkylation of the ambident enolates of a methyl glycinate Schiff base with ethyl chloride was studied at B3LYP and MP2 levels with $6-31+G^*$ basis set. The free (E)-enolates and (Z)-enolate are similar in energy and geometry. The transition states for the alkylation of the free (E)/(Z)-enolate with ethyl chloride have similar energy barriers of ~13 kcal/mol. However, with a lithium ion, the (E)-enolate behaves as an ambident enolate and makes a cyclic lithium-complex in bidentate pattern which is more stable by 11-23 kcal/mol than the (Z)-enolate-lithium complexes. And the TS for the alkylation of (E)-enolate-lithium complex coordinated with one methyl ether is lower in energy than those from (Z)-enolate-lithium complexes by 4.3-7.3 kcal/mol. Further solvation model (SCRF-CPCM) and reaction coordinate (IRC) were studied. This theoretical study suggests that the alkylation of ambident enolates proceeds with stable cyclic bidentate complexes in the presence of metal ion and solvent.

4-Chloro-2-((E)-(Isopropylimino)methyl)phenol 코발트(II) 착물에 대한 결정 구조 및 열분해 연구 (Crystal Structure and Thermal Decomposition Studies on Cobalt (II) Complex of 4-Chloro-2-((E)-(Isopropylimino)methyl)phenol)

  • Pu, Xiao-Hua
    • 대한화학회지
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    • 제55권3호
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    • pp.341-345
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    • 2011
  • Schiff base 코발트(II) 착물, bis[4-chloro-2-((E)-(isopropylimino) methyl) phenol]cobalt(II), 을 합성하고 단결정 X-ray 회절 분석을 하였다. 코발트 (ii) 합성물의 현상학적, 속도론적 및 기계적 특성은 TG/DTG법으로 연구하였다. 실험 데이터에 기초하여, 활성화 에너지, 지수 앞자리인자, 활성화 엔트로피와 같은 속도론적 파라미터를 계산하였으며, 가장 가능성 있는 메카니즘 함수로는 $g({\alpha})={\alpha}^2$이 추정되었다. 따라서, 모든 분해 단계에서 속도 조절 단계는 1차원 확산 과정(Parabolic model) 이다.

Tetrameric Self-Assembly of a Cu(II) Complex Containing Schiff-Base Ligand and Its Unusually High Catecholase-like Activity

  • Sarkar, Shuranjan;Lee, Woo Ram;Hong, Chang Seop;Lee, Hong-In
    • Bulletin of the Korean Chemical Society
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    • 제34권9호
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    • pp.2731-2736
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    • 2013
  • We report a new tetrameric supramolecular Cu(II) complex ($Cu_4L_4$ = tetrakis(N,N'-bis(salicylidene)-2,2'-ethylenedianiline)Copper(II)) with a Schiff-base ligand ($H_2L$ = N,N'-bis (salicylaldimine)-1,2-ethylenediamine) containing two N,O-bidentate chelate groups. Though the copper sites of $Cu_4L_4$ are non-coupled, the complex exhibits a unsually high catecholase-like activity ($k_{cat}=935h^{-1}$) when the $Cu_4L_4$ solution is treated with 3,5-di-tert-butylcatechol (3,5-DTBC) at basic condition in the presence of air. Combined information obtained from UV-VIS and EPR measurements could lead the suggestion of the reaction pathway in which the substrate may bind to Cu(II) ions by anti-anti didentate bridging mode.