• Title/Summary/Keyword: Co(III) 착물

Search Result 60, Processing Time 0.025 seconds

Electrochemical Properties of Cobalt(II) Schiff Base Complexes in Nonaqueous Solvent (비수용매에서 Schiff Base를 가진 Cobalt(II) 착물들의 전기화학적 성질)

  • Oh, Jeong-Geun;Choi, Yong-Kook
    • Analytical Science and Technology
    • /
    • v.15 no.2
    • /
    • pp.97-101
    • /
    • 2002
  • Co(II) complexes with tridentate Schiff base-NOIPH and tetradentate Schiff base-$NOTDH_2$ and $TNBPH_4$ were synthesized. The redox process of the complexes in DMF solution containing 0.1M TBAP was investigated at glassy carbon electrode by cyclic voltammetry and differential pulse voltammetry techniques. Reduction step of [Co(II)$(NOIP)_2$] and [Co(II)$(H_2O)_2$] complexes were observed in two step as one electron process of irreversible or quasi-reversible and diffusion-controlled reaction. [$Co(II)_2$(TNBP)] complex was observed in one step as one electron process of quasi-reversible and diffusion-controlled reaction.

Structure and Chemical Reactivity of the Transition Metal Complexes (I). Synthesis and Geometrical Isomerism of the Ethylenediamine-triacetatocobalt (III) Complexes with Ammine or Diamines (전이금속착물의 구조와 그 반응성 (I). 암민류를 포함하는 Ethylenediamine-triacetatocobalt (III) 착물의 합성과 기하이성질현상)

  • Dong-Jin Lee;Bong-Gon Kim;Myung-Ki Doh
    • Journal of the Korean Chemical Society
    • /
    • v.29 no.5
    • /
    • pp.516-521
    • /
    • 1985
  • Ethylenediamine-triacetatocobalt (III) complexes with an ammine, an ethylene-diamine, and a trimethylenediamine as the unidentate ligand were prepared, and were isolated as only one isomer for each case by the Dowex 50W-X8, cation exchange resin in $H^+$ form. The geometrical isomer of these complexes have been assigned cis-equatorial form in the three possible geometrical isomers from the elemental analysis, pH titration, IR, NMR, and electronic absorption spectrum. It was found that $[CoN_3O_3]$ system of the meridional form with multidentate ligand have the first absorption band of the largely splitting pattern, and that the diamines (ethylenediamine, trimethylenediamine) have coordinated to the central cobalt (III) ion as a unidentate ligand.

  • PDF

Light-Induced Electron Transfer Reactions in FeⅡ-CoⅢ Binuclear Complexes ($Fe^{II}-Co^{III}$이핵착물의 광유발 전자이동반응)

  • Lee, Gyu Hwan
    • Journal of the Korean Chemical Society
    • /
    • v.38 no.8
    • /
    • pp.598-602
    • /
    • 1994
  • Light-induced electron transfer reaction within binuclear complex $(NC)_5FeII-L-CoIII(NH_3)_5$ was studied with steady-state photolysis and the rate constants were measured for various bridging lignands. klight and quantum yields for BP, PHEN, DAP having conjugation between metal binding sites were about $3{\times}10^{-2} sec^{-1}$ and 1, and for BPEA having no conjugation were about $2{\times}10^{-4} sec^{-1}$ and 0.03. Light-induced electron transfer reaction within binuclear complex was proved to be the chemical mechanism which had charge transfer excited state MLCT*.

  • PDF

Synthesis and Reactions of Organoruthenium(Ⅲ) Complexes (새로운 3가 유기루테늄 착물의 합성과 반응)

  • Lee Dong-Hwan;Kim Hag-Gu;Seo Dae-Ryong;Kim Byung-Soon
    • Journal of the Korean Chemical Society
    • /
    • v.37 no.1
    • /
    • pp.98-104
    • /
    • 1993
  • The paramagnetic organoruthenium(III) complexes $({\eta}^5-C_5Me_5)RuCl_2(PR_3) (PR_3 = PMe_3,\;PEt_3,\;PiPr_3,\;PCy_3,\;PMe_2Ph,\;PMePh_2,\;PPh_3,\;P(p-C_6H_4CH_3)_3$, DPPE, DPPB, Py) (2a∼2k) were synthesized by the reaction of $[({\eta}^5-C_5Me_5)RuCl_2]_2$ (1) with 1 equivalent of the corresponding phosphines $(PR_3)$. The effective magnetic moment ((${\mu}_{eff} = 1.65∼2.07 B.M.$)) derived from the magnetic susceptibility measurements of the complexes (2a∼2k) were consistent with the presence of a "single" unpaired electron in the molecule. Treatment of dichlororuthenium (III) complex ({\eta}^5-C_5Me_5)RuCl_2(PR_3)$ (2) (i) with KBr in acetone afforded the dibromoruthenium (III) complex $({\eta}^5-C_5Me_5)RuBr_2(PR_3) (PR_3 = PPh_3)$, (ii) with sodium amalgam in diethylether led to the bis(phosphine) derivatives $({eta}^5-C_5Me_5)RuCl(PR_3)_2 (PR_3 = PMe_3,\;PMePh_2)$, and (iii) with carbonmonoxide gave to the carbonyl derivatives $({\eta}^5-C_5Me_5)RuCl(PR_3)(CO) (PR_3 = PMe_3,\;PPh_3)$.

  • PDF

Catalytic Effects of Co(Ⅲ) Complexes on the Hydrolysis of p-Nitrophenyl Picolinate (p-Nitrophenyl Picolinate의 가수분해에 대한 코발트(Ⅲ) 착물의 촉매효과)

  • Noh, Jae Geun;Kim, Chang Suk;Hong, Soon Yung
    • Journal of the Korean Chemical Society
    • /
    • v.40 no.4
    • /
    • pp.254-263
    • /
    • 1996
  • Five cobalt(Ⅲ) complexes were synthesized from bi- or tridentate nitrogen ligands. Catalytic actions of these complexes for hydrolyses of p-nitrophenyl picolinate, p-nitrophenyl nicotinate, and p-nitrophenyl isonicotinate were investigated by a spectrophotometric method. p-Nitrophenyl picolinate showed the most senstive reaction among three substrates by these catalysts. Aquohydroxo Co(Ⅲ) complexes raised as much as 21∼40 times the rate of hydrolysis of p-nitrophenyl picolinate at pH 6.5. Activities of complexes were in the order: Co(ibpn)(OH)2(OH2) > Co(aepn)(OH)2(OH2) > Co(tn)2(OH)(OH2) > Co (bpy)2(OH)(OH2) > Co(dien)(OH)2(OH2). Catalytic hydrolysis was postulated to proceed through a intramolecular general base catalysis path which is mixed by a partial intramolecular nucleophilic catalysis.

  • PDF

Stereoselective Electron-Transfer Reaction between Optical Active Cobalt(III) Complex and Racemic Cobalt(II) Complex (광학활성 코발트 (III) 착물과 라세미-코발트(II) 착물간의 입체선택적 전자전달반응)

  • Dong-Jin Lee;Maeng-Jun Jung;Myung-Ki Doh
    • Journal of the Korean Chemical Society
    • /
    • v.35 no.5
    • /
    • pp.500-505
    • /
    • 1991
  • The stereoselectivity on the electron-transfer reaction between optical active ${\bigwedge}$-[CO(EDDS)]- and conformationally restricted complex $[Co({\pm}chxn)_3]^{2+}$ has been examined in aqueous solution. The products are four conformational isomers $(lel_3,\;lel_2ob,\;lelob_2,\;and\;ob_3)$ of ${\bigwedge}$-[Co(chxn)$_3]^{3+}$ with optical purities of 22% e.e, 25% e.e, 11% e.e, and 10% e.e, respectively. The reaction between ${\bigwedge}$-[CO(EDDS)]- and $[Co({\pm}chxn)_3]^{2+}$ in DMSO produced lel3-${\Delta}$ and lel2ob-${\Delta}$-[Co(chxn)$_3]^{3+}$ whose optical purities are 100% e.e, and 75% e.e, respectively.

  • PDF

Reversed-Phase Liquid Chromatographic Separation of Metal Ions by Chelate Formation with 1-(2-Pyridylazo)-2-Naphthol (역상 액체크로마토그래피에 의한 1-(2-Pyridylazo)-2-Naphthol과 킬레이트를 형성하는 금속이온의 분리)

  • Kang, Sam Woo;Park, Sun Ja
    • Journal of the Korean Chemical Society
    • /
    • v.42 no.2
    • /
    • pp.197-202
    • /
    • 1998
  • 1-(2-Pyridylazo)-2-Naphthol (PAN) has been widely used as a spectrophotometric reagent and metallochromic indicator for many metal ions. In this work, the chelate reagent of PAN was used as mobile phase additive for the separation of metal ions by reversed phase chromatography. Metal ions could be detected by monitoring the effluent at 570 nm with spectrophotometric detector. In order to investigate retention behaviors of the metal ions, the chromatograms and capacity factors were obtained as the variation of pH, ionic strength and composition of organic modifier in mobile phase. Under the obtained optimum conditions, the mixtures of Fe(III), Ni(II), Cu(II), Zn(II) and Co(II) could be separated successfully and the calibration curves under the recommended conditions showed an excellent linearity. The detection limits(S/N) were feasible at the nanogram level.

  • PDF

Electrochemical Propertics and Oxidation Reaction of Hydrazobenzene by Oxygen Adducted Tetradentate Schiff Base Cobalt(II)(3MeOSED) Activated Catalyst in Aprotic Solvents(I) (비수용매에서 산소첨가된 네자리 Schiff Base Cobalt(II)(3MeOSED) 활성촉매에 의한 Hydrazobenzene의 산화반응과 전기화학적 성질 (제 1 보))

  • Ki-Hyung Chjo;Yong-Kook Choi;Sang-Bock Kim
    • Journal of the Korean Chemical Society
    • /
    • v.36 no.2
    • /
    • pp.261-272
    • /
    • 1992
  • Tetradentate Schiff base Cobalt(II)(3MeOSED)$(H_2O)_2$ complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(III) complexes such as ${\mu}$-peroxo type [Co(III)(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$in DMF and DMSO or superoxo type [Co(III)(3MeOSED)(Py)]$O_2$ in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of $O_2^-$in 1 : 1 oxygen adducted superoxo type [Co(III)(3MeOSED)(Py)]$O_2$complex and three steps not including prewave of $O_2^-$ in 1 : 2 oxygen adducted ${\mu}$-peroxo type [Co(III)-(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$. A superoxo type [Co(III)(3MeOSED)(L)]$O_2\;(L: CH_3OH)$ was generated with oxygen in methanol. Selectively oxidized hydrazobenzene $(H_2AB)$ to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is $(2.96 {\pm} 0.2)$${\times}$ $10^{-1}$M/sec. $H_2AB$ + Co (II)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.

  • PDF

Studies on the Synthesis of Cobalt(III) Complexes with Quadridentate (네자리 리간드를 갖는 코발트(III) 착물에 관한 연구)

  • Oh, Joon-Suk;Lee, Won
    • Journal of the Korean Chemical Society
    • /
    • v.12 no.1
    • /
    • pp.12-17
    • /
    • 1968
  • A series of octahedral cobalt(III) complexes involving quadridentate bissalicylaldehyde ethylenediimine (SAED) chelating ligand have been prepared as a new compound: [$Co(SAED)X_2]^+,$ where X = ammonia, pyridine, and bidentate ethylenediamine. Properties and configuration of the complexes were studied by the chemical and physical method.

  • PDF

Synthesis Catalytic Application of Several$d^8Transition Metal Diphosphine Complexes, (MCl_2PP) (M = Ni^{2+}, Pd^{2+}, Pt^{2+}, Au^{3+} ; PP = diphosphines)$ (몇가지 $d^8$ 전이금속-디포스핀 착물 ($MCl_2PP$)의 합성과 촉매적 응용 (M = $Ni^{2+}$, $Pd^{2+}$, $Pt^{2+}$, $Au^{3+}$ ; PP = diphosphines))

  • Park Yu-Chul;Kim Kyung-Chae;Cho Young-Jae
    • Journal of the Korean Chemical Society
    • /
    • v.36 no.5
    • /
    • pp.685-691
    • /
    • 1992
  • The $d^8$-transition metal complexes containing diphosphine, $MCl_2PP$ were prepared by using $K_nMCl_m$ as starting materials, wherein M were Ni(II), Pd(II), Pt(II) and Au(III) and PP were bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)ethane(dppe), bis(diphenylphosphino)propane (dppp) and bis(diphenylphosphino)ethylene(dppety). The complexes were characterized by the spectral property $(^H-NMR$, $^{31}P-NMR$ and UV-Visible spectra) together with elemental analysis. The complexes were tested for the catalytic activity on the formation reactions of 3(2H)-furanone and cyclic carbonate. The only Ni(II)- and Pd(II)-diphosphine complexes displayed a good catalytic effects in the production of 3(2H)-furanone from 2-methyl-3-butyn-2-ol [reaction (1)]. But all the diphosphine complexes as catalyst were almost inactive towards cyclic carbonate production preaction [reaction (2)].

  • PDF