• Title/Summary/Keyword: Co(III) complex

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Cobalt(III) Complex of Ethylenediamine-N,N'-di-${\alpha}$-Isobutyric Acid (Ethylenediamine-N,N'-di-${\alpha}$-Isobutyric Acid의 코발트(III) 착물)

  • Moo-Jin Jun;Chang-Yoon Han;Chang-Woo Park;Sung Rack Choi;Kwang-Ha Park
    • Journal of the Korean Chemical Society
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    • v.30 no.1
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    • pp.84-89
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    • 1986
  • A newflexible $N_2O_2$-type tetradentate ligand. Ethylenediamine-N,N'-di-${\alpha}$-isobutyric acid(eddib), has been synthesized, and dichloro cobalt(III) complex of eddib has been prepared via the air-oxidation technique. Only S-cis isomer has been yielded during the preparation of complex. Ring strain and steric hinderance are cited as the cause for the preference for the S-cis geometric configuration. On series of cobalt(III) complexes of eddib, $[Co(eddib)L]^{n+}$ $(L = Cl{\cdot}(H_2O),\;CO_3^{2-},\;(H_2O)_2)$have been prepared in situ. In their electronic absorption spectra, the absorption maxima and their intensities of the above series of complexes are on the ordinary line of the spectrochemical and hyperchromic series. Elemental analysis, IR, NMR and electronic absorption spectra have been used to characterize the complex and geometries of the complex.

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The Comparison of Sintering Characteristics between the PVA-Al(III) Complex added $UO_2$Pellet and AlOOH added $UO_2$pellet (PVA-Al(III) 착물 첨가 $UO_2$소결체와 AlOOH 첨가 $UO_2$소결체의 소결 특성 비교)

  • Lee, Sin-Yeong;Yu, Ho-Sik;Lee, Seung-Jae;Kim, Hyeong-Su;Bae, Gi-Gwang
    • Korean Journal of Materials Research
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    • v.10 no.1
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    • pp.55-61
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    • 2000
  • The sintering characteristics of PVA-Al(III) complex added $UO_2$ pellet and AlOOH added $UO_2$pellet were compared. The major phase of PVA-Al(III) complex and AlOOH decomposed at $1000^{\circ}C$ in $H_2$atmosphere was $\theta-Al_2O_3$. Compared with the apparent density of pure $UO_2$, that of AlOOH added $UO_2$ powder was higher but that of PVA-Al(III) complex was lower. the densification of AlOOH added $UO_2$ pellet was initiated at about $800^{\circ}C$, the densification of PVA-Al(III) complex added $UO_2$ pellet was initiated at about $900^{\circ}C$ respectively. In a view of pore size distribution, the PVA-Al(III) complex added $UO_2$ pellet appeared as monomodal type, whereas the AlOOH added $UO_2$ pellet appeared as bimodal type. The grain size of AlOOH added $UO_2$ pellet was about $13\mu\textrm{m}$ but the grain size of PVA-Al(III) complex added $UO_2$ pellet was increased up to about $36\mu\textrm{m}$.

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Preparation and Characterization of Half-Sandwich Cobalt(III) Complexes of Cp Ligands with a Rigid Thioanisole Side-Chain

  • S, Sujith;Lee, Bun-Yeoul;Han, Jin-Wook
    • Bulletin of the Korean Chemical Society
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    • v.28 no.8
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    • pp.1299-1304
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    • 2007
  • New sulfur functionalized cyclopentadiene ligands, 1-[2-(thioanisole)]-2,5-dimethylcyclopentadiene (3), 1-[2- (thioanisole)]-2,3,5-trimethylcyclopentadiene (4), and 1-[2-(thioanisole)]-2,3,4,5-tetramethylcyclopentadiene (5), were prepared. In these ligands, the S-donor atom is connected to a cyclopentadiene ring by a rigid phenylene spacer. CpCo(III)-diiodo half-sandwich complexes (6-8) were obtained from reaction the ligands (3- 5) with Co2(CO)8, followed by treatment of I2. Substitution reaction of CpCo(III)-diiodo complexes with MeLi yielded the corresponding CpCo(III)-dimethyl complexes (9-11). Further transformation to the corresponding cationic cobalt complexes (12-14) were achieved by reaction of the CpCo(III)-dimethyl complexes with HB(ArF)4·2Et2O and trapping with CD3CN. The new sulfur functionalized cyclopentadiene ligands having a rigid phenylene spacer and the corresponding cobalt complexes were characterized by 1H, 13C and 19F NMR spectroscopy. The diiodo Complex 6 was also characterized by a single crystal X-ray diffraction method.

Racemization of Optical Active tris-Oxalatocobaltate (III) Ion in Mixed Solvants (혼합용매내에서 광학활성인 tris-Oxalatocobaltate (III) ion의 라세미화에 관한 연구)

  • Dong Jin Lee;Doh Myung Ki
    • Journal of the Korean Chemical Society
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    • v.30 no.4
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    • pp.377-382
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    • 1986
  • Racemic tris-oxalatocobaltate (III) complex ions were optically resolved by an optical active complex, ${\Delta}$-tris-ethylenediamine cobalt (III), and then racemization of ${\bigwedge}-[Co(ox)_3]^{3-}$ obtained was investigated in various mixed solvent such as water-organic solvent (organic solvents=ethanol, iso-propyl alcohol, acetone, and dioxane). The rate of racemization was increased with following order; water < ethanol < acetone < isopropyl alcohol < dioxane; which is the same order for polarizability of organic solvent added. Considering ${\Delta}H^{\neq},\;{\Delta}S^{\neq}$ and above facts for the racemization of ${\bigwedge}-[Co(ox)_3]^{3-}$, it seems to be twist mechanism of plausible mechanisms.

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Stereoselective Ligand Exchange Reaction of trans-dichlorocobalt(III) complex contained SS-epm and racemi propane-1,2-diamine (SS-epm이 배위된 trans-dichlorocobalt(III) 착물과 라세미 propane-1,2-diamine과의 입체선택적 리간드 치환반응)

  • Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.3 no.1
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    • pp.77-82
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    • 2000
  • The stereoselective ligand exchange reaction of trans-$[Co(SS-epm)Cl_2]^+$ and racemic propane-1,2-diamine (rac-pn) produces the complex that is identified as $[CO(N)_6]^{3+}$ type of $[Co(SS-epm)(pn)]^{3+}$ by absorption spectrum. It is conceivable that the reaction mechanism involves substitution and isomerization. The calculated and experimentally determined ratios of the complexed enantiomeric substrates at equilibrium were as follows: $[Co(SS-epm)(pn)]^{3+}$,calcd 32 % / 68 %, exptl 19 % / 81 % R-pn / S-pn. It has been shown that the employment of molecular mechanics calculations as a predictive tool may lead to the design of chiral complexes that may be applied to the separation of racemic mixtures of simple bidentate ligands.

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Electrochemical and Spectroelectrochemical Studies of Cobalt Salen and Salophen as Oxygen Reduction Catalysts

  • Bertha Ortiz;Park, Su Mun
    • Bulletin of the Korean Chemical Society
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    • v.21 no.4
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    • pp.405-411
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    • 2000
  • Electrochemical and spectroelectrochemical studies of cobalt-Schiff (Co-SB) base complexes, Co(salen) [N-N'-bis(salicylaldehyde)-ethylenediimino cobalt(II)] and Co(salophen) [N-N'-bis(salicylaldehyde)-1,2-pheny-lenediimino cobalt(II)], have been c arried out to test them as oxygen reduction catalysts. Both compounds were found to form an adduct with oxygen and exhibit catalytic activities for oxygen reduction. Comparison of spec-tra obtained from electrooxidized complexes with those from Co-SB complexes equilibrated with oxygen in-dicates that the latter are consistent with the postulated complex formed with oxygen occupying the coaxial ligand position, namely, Co(III)-SB·O2 - .The catalysis of oxygen reduction is thus achieved by reducing Co(III) in the oxygen-Co-SB adduct, releasing the oxygen reduction product, e.g., O2 - ., from the Co(II)-SB complex.

Synthesis and Crystal Structure of Cobalt(III) Complex with Chiral Pentadentate Bis-Amide Ligand, 1,9-bis(S)-pyrrolidinyl-2,5,8-triazanonane-1,9-dione$(S,S-prodienH_2)$

  • 이배욱;오창언;도명기
    • Bulletin of the Korean Chemical Society
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    • v.19 no.4
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    • pp.457-462
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    • 1998
  • A chiral pentadentate bis-amide ligand, 1,9-bis(S)-pyrrolidinyl-2,5,8-triazanonane-1,9-dio ne$(S,S-prodienH_2)$ has been synthesized from the reaction of bis(2-aminoethyl)amine(dien) and S-proline, and the structure of $[Co(S,S-prodien)H_2O]ClO_4$ has be en determined by single crystal X-ray diffraction. The geometrical structure of the Co(III) complex has been an αβ -form, where the dien moiety of ligand chelates to a facial in metal center, and the aqua ligand coordinates a cis site to the secondary nitrogen of dien. The Co-N(1), Co-N(3) distances of two amide moiety in S,S-prodien are shorter than the other Co-N(2), Co-N(4), and Co-N(5) distances because of the increased basicity of nitrogen in amide. The complex crystallizes in the monoclinic space group $P2_1$(#4), with a=7.838(1), b=12.675(1), c=9.710(1) Å, β=100.39(1) and z=2. Refinement gives the final R and $R_w$ values of 0.045 and 0.057, respectively for 2130 observed reflections. Based upon the CD and X-ray data, it is identified that the absolute configuration of the αβ -$[Co(S,S-prodien)H_2O]ClO_4$ has a Λ-form.