• 제목/요약/키워드: Schiff-Base ligands

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Synthesis and Physicochemical Properties of Schiff Base Macrocyclic Ligands and Their Transition Metal Chelates

  • Rafat, Fouzia;Siddiqi, K.S.
    • 대한화학회지
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    • 제55권6호
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    • pp.912-918
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    • 2011
  • Tetraaza Schiff base macrocyclic ligands, $L^1$,$L^2$ and their transition metal chelates have been synthesized and characterized by elemental analyses, IR, electronic, EPR and $^1H$ NMR spectra, TGA and magnetic measurements. The molar conductance of one milli-molar solution of the complexes measured in DMF indicates that the divalent metal complexes are nonelectrolyte while those of trivalent metal ion, are 1:1 electrolytic in the same solvent. The reduction of Racah parameter from the free ion value confirms the presence of considerable covalence of metal ligand sigma bond in the Co(II) and Mn(II) complexes. The EPR spectra of Cu(II) complexes at room temperature shows axial symmetry indicating a $d_x{^2}_{-y}{^2}$ ground state with significant covalent character. The thermal analysis suggests that the complexes do not contain water molecules because only the metal is left as residue.

여러자리 질소-산소계 시프염기 리간드와 전이금속착물의 합성 및 특성 (Synthesis and Properties of Polydentate Schiff Base Ligands having $N_nO_2$ (n=3~5) Donor Atoms and their Transition Metal Complexes)

  • 김선덕;신윤열;박성우
    • 분석과학
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    • 제11권5호
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    • pp.366-373
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    • 1998
  • 여러자리 시프염기인 BSDT(1,9-bis(2-hydroxyphenyl)-2,5,8-triaza-1,8-nonadiene), BSTT(1,12-bis(2-hydroxyphenyl)-2,5,8,11-tetraaza-1,11-dodecadiene)와 BSTP(1,15-bis(2-hydroxyphenyl)2,5,8,11,14-pentaaza-1,14-pentadodecadiene)를 합성하여 전위차적정법으로 산해리 상수값을 구하고, DMSO 용매에서 이들 리간드들과 구리(II), 니켈(II), 및 아연(II)등의 전이금속과의 안정도 상수값을 폴라로그래피를 이용하여 구하였다. 이때 금속과 리간드는 1:1착물을 형성하였고, 안정도 상수값은 금속으로서는 Cu(II)>Ni(II)>Zn(II) 순서로, 리간드로서는 BSTP>BSTT>BSDT 순서로 나타남으로서 주개 원자수의 증가에 의존한다는 사실을 알았다. 엔탈피와 엔트로피는 모두 음의 값을 나타내었는데 흡열반응으로서 금속이온과 리간드가 매우 강하게 결합하고 있음을 알 수 있고 극성을 가지는 금속착물이 생성되어 용매인 DMSO와 아주 강한 상호작용을 함으로써 큰 음의 엔트로피 값을 가진 것으로 생각된다.

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Synthesis, Characterization and Antimicrobial Activity of Zirconium (IV) Complexes

  • Sharma, Shobhana;Jain, Asha;Saxena, Sanjiv
    • 대한화학회지
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    • 제56권4호
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    • pp.440-447
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    • 2012
  • Heteroleptic complexes of zirconium (IV) derived from bulky Schiff base ligands containing a sulphur atom and oximes of heterocyclic ${\beta}$-diketones of the general formula ZrLL' (where $LH_2=RCNH(C_6H_4)SC:C(OH)N(C_6H_5)N:CCH_3$, $R=-C_6H_5$, $-C_6H_4Cl(p)$ and $L^{\prime}H_2=R^{\prime}C:(NOH)C:C(OH)N(C_6H_5)N:CCH_3$, $R^{\prime}=-CH_2CH_3$, $-C_6H_5$, $-C_6H_4Cl(p)$ were prepared by the reactions of zirconium tetrachloride with disodium salts of Schiff bases ($L\;Na_2$) and oximes of heterocyclic ${\beta}$-diketones ($L^{\prime}\;Na_2$) in 1:1:1 molar ratio in dry refluxing THF. The structures of these monomeric zirconium (IV) complexes were elucidated with the help of elemental analysis, molecular weight measurements, spectroscopic (IR, NMR and mass) studies. A distorted trigonal bipyramidal geometry may be suggested for these heteroleptic zirconium (IV) complexes. The ligands (bulky Schiff base ligands containing a sulphur atom and oximes of heterocyclic ${\beta}$-diketones) and their heteroleptic complexes of zirconium (IV) were screened against A. flavus, P. aeruginesa and E. coli.

Spectral, Electrochemical, Fluorescence, Kinetic and Anti-microbial Studies of Acyclic Schiff-base Gadolinium(III) Complexes

  • Vijayaraj, A.;Prabu, R.;Suresh, R.;Kumari, R. Sangeetha;Kaviyarasan, V.;Narayanan, V.
    • Bulletin of the Korean Chemical Society
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    • 제33권11호
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    • pp.3581-3588
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    • 2012
  • A new series of acyclic mononuclear gadolinium(III) complexes have been prepared by Schiff-base condensation derived from 5-methylsalicylaldehyde, diethylenetriamine, tris(2-aminoethyl) amine, triethylenetetramine, N,N-bis(3-aminopropyl)ethylene diamine, N,N-bis(aminopropyl) piperazine, and gadolinium nitrate. All the complexes were characterized by elemental and spectral analyses. Electronic spectra of the complexes show azomethine (CH=N) within the range of 410-420 nm. The fluorescence efficiency of Gd(III) ion in the cavity was completely quenched by the higher chain length ligands. Electrochemical studies of the complexes show irreversible one electron reduction process around -2.15 to -1.60 V The reduction potential of gadolinium(III) complexes shifts towards anodic directions respectively upon increasing the chain length. The catalytic activity of the gadolinium(III) complexes on the hydrolysis of 4-nitrophenylphosphate was determined. All gadolinium(III) complexes were screened for antibacterial activity.

여러자리 시프 염기 리간드와 구리(Ⅱ) 착물의 합성과 성질 (Syntheses and Properties of Polydentate Schiff Base and Their Cu(Ⅱ) Complexes)

  • 김선덕;신윤열;장기호
    • 대한화학회지
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    • 제38권4호
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    • pp.319-327
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    • 1994
  • 질소원자를 네 개 또는 다섯 개 가지는 트리에틸렌테트라아민과 테트라에틸렌펜타아민에 살리실알데히드를 각각 반응시켜 황갈색 액체상의 여섯자리 배위자리를 가지는 새로운 시프 염기 리간드인 비스(살리실알데히드)-트리에틸렌테트라아민(BSTT)과 일곱자리 시프 염기인 비스(살리실알데히드)-테트라에틸렌펜타아민(BSTP)을 합성하고, 다시 이들 액체상의 시프 염기에 아세트산과 진한 염산을 가하여, pH4.0의 특정한 농도하에서 연노란색의 염산염 시프 염기들의 결정을 얻었다. 또한 이들 시프 염기 리간드와 구리(Ⅱ)를 반응시켜 새로운 시프 염기-구리(Ⅱ)착물을 합성하여 여러가지 물리적 및 화학적 성질에서부터 가능한 이들 화합물의 구조를 제안하였다.

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단핵 및 이핵성 시프염기리간드 Cu(II) 착물의 특성과 Ascorbic Acid에 대한 산화반응 (Properties of Mononuclear and Binuclear Cu(II) Schiff Base Complexes and Oxidation of Ascorbic Acid)

  • 김선덕;이영석;박정은
    • 분석과학
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    • 제13권5호
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    • pp.558-564
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    • 2000
  • 단핵성 네자리 시프염기인 N,N'-bissalicylidene-1,2-phenylenediamine(BSPD)와 이핵성 네자리 시프 염기 리간드인 N,N',N'',N'''-tetrasalicylidene-3,3',4,4'-tetraaminodiphenyl-methane (TSTM) 및 N, N',N'',N'''-tetrasalicylidene-3,3'-diaminobenzidine (TSDB)을 합성하고, 이들 리간드의 양성자 해리상수를 전위차법으로 구하였다. 합성된 시프염기 리간드들과 Cu(II) 이온을 이용해 착물을 합성하여 순환전압-전류법으로 착물의 특성을 측정한 결과 $Cu(II)_2$-TSTM 착물은 순환전압-전류법에서 두 과정 두 단계의 환원과정으로 두 전자의 확산 지배적인 과정으로 일어남을 알았다. 또한 단핵성 착물 Cu(II)-BSPD와 이핵성 착물 $Cu(II)_2$-TSDB 및 $Cu(II)_2$-TSTM을 ascorbic acid의 산화반응에 이용한 결과, 반응속도는 $Cu(II)_2$ -TSTM>$Cu(II)_2$-TSDB>Cu(II)-BSPD의 순으로 이핵성인 $Cu(II)_2$-TSTM 착물이 가장 큰 값을 가짐을 알았다.

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Synthesis and Crystal Structures of Copper(II) Complexes with Schiff Base Ligands: [Cu2(acpy-mdtc)2(HBA)(ClO4)]·H2O and [Cu2(acpy-phtsc)2(HBA)]·ClO4

  • Koo, Bon Kweon
    • Bulletin of the Korean Chemical Society
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    • 제34권11호
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    • pp.3233-3238
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    • 2013
  • Two new Cu(II) complexes, $[Cu_2(acpy-mdtc)_2(HBA)(ClO_4)]{\cdot}H_2O$ (1) (acpy-mdtc- = 2-acetylpyridine S-methyldithiocarbamate and $HBA^-$ = benzilic acid anion) and $[Cu_2(acpy-phtsc)_2(HBA)]{\cdot}ClO_4$ (2) (acpy-$phtsc^-$ = 2-acetylpyridine 4-phenyl-3-thiosemicarbazate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are dinuclear copper(II) complexes bridged by two thiolate sulfur atoms of Schiff base ligand and bidentate bridging $HBA^-$ anion. For 1, each of the two copper atoms has different coordination environments. Cu1 adopts a five-coordinate square-pyramidal with a $N_2OS_2$ donor, while Cu2 exhibits a distorted octahedral geometry in a $N_2O_2S_2$ manner. For 2, two Cu(II) ions all have a five-coordinate square-pyramidal with a $N_2OS_2$ donor. In each complex, the Schiff base ligand is coordinated to copper ions as a tridentate thiol mode.