• 제목/요약/키워드: Bidentate ligand

검색결과 52건 처리시간 0.022초

Cu Catalyst System with Phosphorous Containing Bidendate Ligand for Living Radical Polymerization of MMA

  • Hong Sung Chul;Shin Ki Eun;Noh Seok Kyun;Lyoo Won Seok
    • Macromolecular Research
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    • 제13권5호
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    • pp.391-396
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    • 2005
  • The polymerization of methyl methacrylate (MMA) was carried out using CuBr/bidentate phosphorus ligand catalyst systems. MMA polymerization with CuBr/phosphine-phosphinidene (PP) exhibited high conversion ($\~80\%$) in 5 h at $90^{\circ}C$ along with a linear increase of ln($[M]_0/[M]$) versus time, indicating constant concentration of the propagating radicals during the polymerization. The molecular weight of the prepared PMMA tended to increase with conversion, suggesting the living polymerization characteristic of the system. On the other hand, a large difference between the measured and theoretical molecular weight and a broad molecular weight distribution were observed, implicating possible incomplete control over the polymerization. This may have been caused by the low deactivation rate constant ($\kappa_{deact}$) of the system. The low $\kappa_{deact}$, would result in irreversible generation of radicals instead of reversible activation/deactivation process of ATRP. Polymerizations performed at different ligand to CuBr ratios and different monomer to initiator ratios did not afford better control over the polymerization, suggesting that the controllability of CuBr/phosphorus ligand system for ATRP is inherently limited.

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

  • 김동엽
    • 한국산업융합학회 논문집
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    • 제3권1호
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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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2,2-비스(메틸아미노메틸)-1,3-dioxolane의 백금(Ⅱ) 착물 (Platinum(II) Complexes of 2,2-bis(Methylaminomethyl)-1,3-dioxolane)

  • 전무진
    • 대한화학회지
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    • 제22권2호
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    • pp.99-104
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    • 1978
  • 새로운 두자리 아민리간드 2,2-bis(메틸아미노메틸)-1,3-dioxolane(mexo)가 합성되었고 이 리간드로부터 디클로로 및 trans-R-cyclohexanediamine(R-chxn) 백금(II) 착물이 합성되었다. 착물은 평면 사각형의 구조이며 원소분석, 핵자기공명, 흡수분광법 및 원편광이색성분광분석을 이용하여 리간드와 착물의 구조를 설명하였다.

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Spectroscopic Properties and Ligand Field Analysis of trans -Dibromo(2,2-dimethyl-1,3-diaminopropane)chromium(III) Moiety

  • Choi, Jong-Ha;Oh, In-Gyung;Lim, Woo-Taik;Ryoo, Keon-Sang;Kim, Dong-Il;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • 제26권6호
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    • pp.903-908
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    • 2005
  • The sharp-line absorption and emission spectra of $(H_{13}O_6)${$trans-[Cr(Me_2tn)_2Br_2]$}$_2Br_2(ClO_4)\;(Me_2$tn = 2,2-dimethyl-1,3-diaminopropane) have been measured between 13000 $cm^{-1}$ and 16000 $cm^{-1}$ at 5 K. The 298 K infrared and visible absorption spectra have also been measured. The nine electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using observed transitions, a ligand field analysis has been performed to probe the ligand field properties of coordinated atoms in the title chromium(III) complex ion. The zero-phonon line in the sharp-line absorption spectrum splits into two components by 286 $cm^{-1}$, and the large $^2E_g$ splitting can be reproduced by the modern ligand field theory. It is confirmed that nitrogen atoms of the Me2tn ligand have a strong $\sigma$-donor character, but the bromide has weak $\sigma$- and $\pi$-donor properties toward chromium(III) ion.

Synthesis and Solution Properties of La(III)-N-ethylmorpholine Complex

  • Anwar, Zeinab M.;Sung, Yong-Kiel
    • Bulletin of the Korean Chemical Society
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    • 제26권4호
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    • pp.614-618
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    • 2005
  • The complex of the composition LaL(N$O_3)_3\;(H_2O)_2$ is prepared by the reaction of La($NO_3)_3{\cdot}6H_2O$ with Nethylmorpholine in aqueous medium. The ligand is involved in the complex as a neutral species where the chelation occurs via the oxygen of the ligand moiety and the nitrate groups as bidentate ligand. The chemical structure of the studied complex is confirmed through IR, XRD, and thermal analysis data. The complexation equilibria of La(III) with N-ethylmopholine is studied in aqueous medium at ionic strength I = 0.1 mol${\cdot}dm^{-3}\;KNO_3$ and at 25, 35 and 45 ${^{\circ}C}$, respectively. The thermodynamic parameters $\Delta$G, $\Delta$H and $\Delta$S values were calculated to prove the association with the complex formation. It is clearly observed that the process is accompanied by absorption of heat, i.e. endothermic process, while the entropy does not change greatly attributed to the release of constant number of water molecules during chelate formation.

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

  • 오준석;이원
    • 대한화학회지
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    • 제12권1호
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    • pp.12-17
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    • 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.

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Syntheses, Spectral, Surface Morphological and Gamma Ray Irradiation Studies of Some Oxomolybdenum(V) and Dioxomolybdenum(VI) Complexes of an Azo Dye Derived from 4-aminoantipyrine

  • Nair, M.L. Harikumaran;Appukuttan, Anju.S.
    • 대한화학회지
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    • 제56권2호
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    • pp.217-227
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    • 2012
  • Syntheses of some novel oxomolybdenum(V) and dioxomolybdenum(VI) complexes with an azo dye methoxyphenolazoantipyrine (HL) derived from 4-aminoantipyrine and 2-methoxyphenol are reported. The complexes have been characterized by elemental analyses, molar conductance, magnetic susceptibility data, IR, UV-Vis, $^1H$ NMR, EPR and FAB mass spectral studies. The physicochemical studies and spectral data indicate that HL acts as a bidentate chelating ligand. The complexes have the general formulae [$MoO(HL)XCl_2$] and [$MoO_2(HL)XCl$],where X=Cl, NCS or $NO_3$. All the complexes are found to have distorted octahedral geometry. Structural and morphological characterization of the complexes [$MoO(HL)Cl_3$](1) and [$MoO_2(HL)Cl_2$](4) before and after gamma ray irradiation,was performed by X-ray diffraction and scanning electron microscopy( SEM).The ligand and the complexes were screened for their possible antimicrobial activities.

Metal Complexes of Enrofloxacin Part I: Preparation, Spectroscopic, Thermal Analyses Studies and Antimicrobial Evaluation

  • El-Shwiniy, Walaa H.;El-Attar, Mohamed S.;Sadeek, Sadeek A.
    • 대한화학회지
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    • 제57권1호
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    • pp.52-62
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    • 2013
  • The interaction of titanium (IV), yttrium (III), zirconium (IV), palladium (II) and cerium (IV) with deprotonated enrofloxacin leads to the formation of the neutral or cationic mononuclear complexes. The isolated solid complexes have been characterized with physicochemical and spectroscopic techniques and thermogravimeteric analyses. The spectroscopic data indicate that the enrofloxacin ligand is on the deprotonated mode acting as bidentate ligand coordinated to the metal ions through the ketone oxygen and a carboxylato oxygen and the metal ions completed the coordination number with water molecules. The thermal decomposition mechanisms proposed for enrofloxacin and their metal complexes were discussed. The activation energies, $E^*$, enthalpies, ${\Delta}H^*$, entropies, ${\Delta}S^*$ and Gibbs free energies, ${\Delta}G^*$, of the thermal decomposition reactions have been derived from thermogravimetric (TG) and differential thermogravimetric (DTG) curves, using Coats-Redfern (CR) and Horowitz-Metzeger (HM) methods. The antimicrobial activity has been evaluated against six different microorganisms.

Magnetic and Spectroscopic Studies of some Oxovanadium(IV) Complexes having O = V(O)$_4$ Chromophore

  • Choi, Sung-Nak;Kim, Young-Inn;Shim, Yoon-Bo;Choo, Hi-Shik;Kim, Young-Jin
    • Bulletin of the Korean Chemical Society
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    • 제10권2호
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    • pp.138-142
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    • 1989
  • Three oxovanadium(IV) complexes with bidentate ligands having only oxygen donor atoms, benzohydroxamic acid (Hben), 8-hydroxyquinoline-N-oxide(Hhqno) and picolinic acid-N-oxide (Hpicn) are prepared and magnetic and spectroscopic properties are investigated for the complexes $VO(ben)_2,\;VO(hqno)_2\;and \;VO(picn)_2.$ Magnetic data together with IR results strongly indicate that dimeric intermolecular interaction is significant in $VO(ben)_2$ while the presence of polymeric V-O${\cdot}{\cdot}$V-O interaction is suggestive in $VO(picn)_2$. For all three complexes, three electronic d-d transitions were observed; extremely strong optical absorption of these bands of $VO(ben)_2$ in DMSO are supposed to be arised from a great metal-ligand covalency. Some fundamental vibration modes of oxovanadium(IV) complexes were empirically assigned from the differences in the spectrum of metal complexes with free ligand.

Isotropic NMR Shifts in Some Pyridine-Type Ligands Complexed with Paramagnetic Undecatungstocobalto(Ⅱ)silicate and Undecatungstonickelo(Ⅱ) silicate Anions. Identifications of Dumbbell-Shaped 4,$4^{\prime}$-Bipyridyl Complexes

  • Moonhee Ko;Gyung Ihm Rhyu;Hyunsoo So
    • Bulletin of the Korean Chemical Society
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    • 제14권4호
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    • pp.500-506
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    • 1993
  • $^1H$ and $^{13}C$ NMR spectra for pyridine, ${\beta}$-and ${\gamma}$-picoline, pyrazine, and 4,4'-bipyridyl complexed with paramagnetic undecatungstocobalto(II)silicate and undecatungstonickelo(II)silicate anions are reported. For these complexes the ligand exchange is slow on the NMR time scale and the pure resonance lines have been observed at room temperature. The isotropic shifts in nickel complexes can be interpreted in terms of contact shifts by ${\sigma}$-electron delocalization. Both contact and pseudocontact shifts contribute to the isotropic shifts in cobalt complexes. The contact shifts, which are obtained by subtracting the pseudocontact shifts from the isotropic shifts, require both ${\sigma}$-and ${\pi}$-electron delocalization from the cobalt ion. Slow ligand exchange has also allowed us to identify the species formed when bidentate ligands react with the heteropolyanions. Pyrazine forms a 1 : 1 complex, while 4,4'-bipyridyl forms both 1 : 1 and dumbbell-shaped 1 : 2 complexes.