• 제목/요약/키워드: N,O-ligand

검색결과 217건 처리시간 0.023초

네자리 리간드-황아미노산 금속착물의 산화반응에 의한 배위된 황원자의 sulfoxide 원자단으로의 전환 (Conversion of Coordinated Sulfur Atom into Sulfoxide Group via Oxidation Reaction of Metal Complexes of Tetradentates and Sulfur Amino Acids)

  • 이숭실;;최승락;전무진
    • 대한화학회지
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    • 제33권5호
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    • pp.516-521
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    • 1989
  • 주게원자가 질소원자와 산소원자인 N2O2형 네자리 리간드 ethylenediamine-N,N'-S-${\alpha}$-isobutylacetic acid(SS-eniba)의 디클로로 로듐(III)$[Rh(SS-eniba)Cl_2]$-의 합성에서 ${\Delta}-s-cis$${\wedge}-uns-cis$ 이성체를 분리하였다. ${\Delta}-s-cis-[Rh(SS-eniba)Cl_2]$- 착물과 S-methyl-L-cystcine(Smc)의 반응으로부터 ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$ 착물을 합성한 다음 $H_2O_2$를 이용한 산화반응으로부터 배위된 황원자가 sulfoxide 원자단으로 산화된 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+(Smc-o=S-methyl-L-cysteine sulfoxide)$ 착물이 형성됨을 관찰하였다. 한편 S-methyl-L-cysteine을 $H_2O_2$와 반응시켜 sulfoxide 원자단으로 산화시킨 S-methyle-L-cysteine sulfoxide의 합성을 별도로 진행한 후 ${\Delta}-s-cis-[Rh(SS-eniba)Cl_2]^+$ 착물에 배위시켜 표준착물인 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+$를 합성한 다음 ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$ 착물을 산화시켜 얻은 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+$착물과 비교하여 배위된 항원자가 sulfoxide 원자단으로 전환되었음을 또한 관찰하였다.

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몇 개의 전이금속 이온과 고분자와 고분자 Complex의 합성과 특성연구 (Synthesis and Characterization of Polymer and Polymer Complex with Some Transition Metal Ions)

  • Badr, S.K.;Mohamed, T.Y.
    • 대한화학회지
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    • 제54권1호
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    • pp.43-48
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    • 2010
  • p-페닐렌 디아민과 maleic anhydride, 아세틸 아세톤과 커플된 O-아미노 페놀의 아조화합물으로 부터 폴리이미드가 만들어졌다. 합성된 폴리이미드(PA)는 DMF용매 속에 다른 몰비율로 녹아있는 $Co^{+2},\;Cr^{+2},\;Ni^{+2},\;Cu^{+2},\;Zn^{+2},\;Cd^{+2}$ and $Fe^{+3}$ 를 포함하는 전이금속이온들의 금속염들과 함께 환류되었다. 이 complex들은 원소분석과 열분석, IR, $^1H$ NMR으로 구조분석, 특성 연구되었다.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part IV); Synthesis and Characterization of Cr(III)-Acetylacetonato, -Malonato and -Oxalato Macrocyclic Complexes

  • Byun, Jong-Chul;Han, Chung-Hun
    • Bulletin of the Korean Chemical Society
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    • 제26권9호
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    • pp.1395-1402
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    • 2005
  • The reaction of cis-[Cr([14]-decane)$(OH)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = acetylacetonate (acac), oxalate (ox) or malonate (mal)} leads to a new cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O\;(1),\;cis-[Cr([14]-decane)(ox)]ClO_4{\cdot}(1/2)H_2O\;(2)\;or\;cis-[Cr([14]-decane)(mal)]ClO_4{\cdot}(1/4)H_2O\;(3)$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two acetylacetonate-oxygen atoms are bonded to the chromium(III) ion in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by $11^{\circ}$ from the ideal value of $180^{\circ}$ for a perfect octahedron. The bond angle O-Cr-O between the chromium(III) ion and the two acetylacetonate-oxygen atoms is close to $90^{\circ}$. The bond lengths of Cr-O between the chromium and the acetylacetonate-oxygen atoms are 1.950(3) and 1.954(2) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 1560 {ν (C=O)}, 1710 {${\nu}_{as}$(OCO)} and 1660 $cm^{-1}$ {${\nu}_{as}$(OCO)} attributed to the acac, ox and mal auxiliary ligands stretching vibrations, respectively.

Polymeric Lead(II)-selective Electrode Based on N,N'-Bis-thiophen-2-ylmethylene-pyridine-2,6-diamine as an Ion Carrier

  • Kim, Hee-Cheol;Lee, Hyo-Kyoung;Choi, A-Young;Jeon, Seung-Won
    • Bulletin of the Korean Chemical Society
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    • 제28권4호
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    • pp.538-542
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    • 2007
  • Polymeric electrodes for lead ion based on N,N'-bis-thiophen-2-ylmethylene-pyridine-2,6-diamine as an ion carrier were prepared. The membrane electrode (m-3) containing o-NPOE as a plasticizer and 50 mol% additive of ionophore gives an excellent Nernstian response (29.59 mV/decade) and the limit of detection of ?log a (M) = 5.74 to Pb2+ in Pb(NO3)2 solution at room temperature. The prepared electrode provided good sensitivity and outstanding selectivity and response for Pb2+ over a wide variety of other metal ions in pH 7.0 buffer solutions. The good sensitivity and selectivity towards lead ion are attributed to the strong complexation of lead ion to N,N'-bis-thiophen-2-ylmethylene-pyridine-2,6-diamine which has geometrically the proper cavity to coordinate to the ligand.

Synthesis, Crystal Structure and Characterization of Cu(II) and Cd(II) Coordination Compounds Based on Ligand 2-(3-(Pyridin-2-yl)-1H-pyrazol-1-yl)acetic Acid

  • Zhang, Ya-Jun;Wang, Cui-Juan;Mao, Kai-Li;Liu, Xiao-Lei;Huang, Shuai;Tong, Yan;Zhou, Xian-Li
    • Bulletin of the Korean Chemical Society
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    • 제35권7호
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    • pp.2086-2092
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    • 2014
  • Two novel coordination compounds $[Cu_2(pypya)_3(H_2O)_2]{\cdot}Cl{\cdot}(H_2O)_5$ (1) and $\{[Cd(pypya)(ta)_{1/2}]{\cdot}H_2O\}_n$ (2) (Hpypya=2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid, $H_2ta$=terephthalic acid) were synthesized and characterized by single X-ray diffraction. Structure determination reveals that complex 1 and complex 2 crystallize in the triclinic system, with the P-1 space group. The asymmetric unit of 1 contains two Cu(II) ions, and their coordination modes are different. These units of complex 1 are linked together via hydrogen bonds and ${\pi}-{\pi}$ interactions, and the 3D structure of complex 1 was formed. Complex 2, a mononuclear Cd(II) coordination compound, has a 2D structure which was constructed via coordination bonds. TGA and fluorescence spectra analysis of complex 1 and complex 2 have also been studied. In addition, the geometry parameters of complex 1 have been optimized with the B3LYP method of density functional theory (DFT) to explain its coordination behavior. The electronic properties of the complex 1 and ligand Hpypya have been investigated based on the nature bond orbital (NBO) analysis at the B3LYP level of theory. The result verifies that the synergistic effect have occurred in the compound.

Microwave-assisted Preparation, Structures, and Photoluminescent Properties of [Ln(NO3)2(H2O)3(L)2](NO3)(H2O) {Ln=Tb, Eu;L=2-(4-pyridylium)ethanesulfonate, (4-pyH)+-CH2CH2-SO3-}

  • Zheng, Zhen Nu;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1859-1864
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    • 2011
  • Two lanthanide complexes, $[Ln(NO_3)_2(H_2O)_3(L)_2](NO_3)(H_2O)$ {Ln = Eu (1), Tb (2); L = 2-(4-pyridylium)-ethanesulfonate, $(4-pyH)^+-CH_2CH_2-SO_3^-)$}, were prepared from lanthanide nitrate and 4-pyridineethanesulfonic acid in $H_2O$ under microwave-heating conditions. Complexes 1 and 2 are isostructural, and the lanthanide metal in both complexes is coordinated to nine oxygen atoms. The pyridyl nitrogen in the ligand is protonated to give a zwitter ion that possesses an $NH^+$ (pyridyl) positive end and an $SO_3^-$ negative end. All O-H and N-H hydrogen atoms participate in hydrogen bonds to generate a two-dimensional (complex 1) or a three-dimensional network (complex 2). Complex 1 exhibits an intense red emission, whereas complex 2 exhibits an intense green emission in the solid state at room temperature.

Anion-Dependent Exocyclic Mercury(II) Coordination Polymers of Bis-dithiamacrocycle

  • Siewe, Arlette Deukam;Kim, Seulgi;Choi, Kyu Seong;Lee, Shim Sung
    • Bulletin of the Korean Chemical Society
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    • 제35권12호
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    • pp.3459-3464
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    • 2014
  • Synthesis and structural characterization of mercury(II) halides and perchlorate complexes (1-4) of bis-$OS_2$-macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type $[Hg(L)X_2]_n$ (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies outside the cavity is six-coordinate with a distorted octahedral geometry, being bound to four adjacent ligands via monodentate Hg-S bonds and two remaining sites are occupied by two terminal chlorido ligands to form a fishnet-like 2D structure. When reacting with mercury(II) iodide, L afforded a 1D coordination polymer $\{[Hg_2(L)I_4]{\cdot}CHCl_3\}_n$ (3) in which each exocyclic Hg atom is four-coordinate, being bound to two sulfur donors from different ligands doubly bridging the ligand molecules in a head-to-tail mode. The coordination sphere in 3 is completed by two iodo terminal ligands, adopting a distorted tetrahedral geometry. On reacting with mercury(II) perchlorate, L forms solvent-coordinated 1D coordination polymer $\{[Hg_2(L)(DMF)_6](ClO_4)_4{\cdot}2DMF\}_n$ (4) instead of the anion-coordination. In 4, the Hg atom is five-coordinate, being bound to two sulfur donors from two different ligands doubly bridging the ligand molecules in a side-by-side mode to form a ribbon-like 1D structure. The three remaining coordination sites in 4 are completed by three DMF molecules in a monodentate manner. Consequently, the different structures and connectivity patterns for the observed exocyclic coordination polymers depending on the anions used are influenced not only by the coordination ability of the anions but also by anion sizes.

몰리브덴의 피리딘계 착물합성과 그 성질 (제1보). 옥소이소티오시아나토몰리브덴 (Ⅴ) 의 치환 피리딘늄염 (Synthesis and Characterization of Substituted Pyridine Complexes of Molybdenum (Ⅰ). Substituted Pyridinium Salts of Oxopentaisothiocyanatomolybdates(Ⅴ))

  • 오상오;김창수
    • 대한화학회지
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    • 제25권3호
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    • pp.177-182
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    • 1981
  • $[MoO(NCS)_5]^{2-}$의 벤조일피리딘늄 및 루티딘늄을 합성한 후 전기전도도, 자기모멘트, 가시 및 적외선스펙트라등에 이하여 이들의 구조를 조사하였다. 옥소오이소티오시아나토몰리브덴(Ⅴ)의 벤조일피리딘늄 및 루티딘늄염에서 티오시아나토의 질소가 몰리브덴과 결합되었으며 벤조일피리딘과 루티딘은 리간드가 아닌 양이온으로 존재함을 확인하였다. 이들 착물은 d-d전이와 전하이동전이가 일어 났으며 착물의 자기모멘트는 ${mu}_{spin-only}$ 값과 거의 같았다.

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Crystal Structure Analysis of 4-Chloro-2{[(2-hydroxy-5-methylphenyl)amino]methyl}5-methylphenol

  • Sharmila, P.;Rajesh, R.;Venkatesan, R.;Ganapathy, Jagadeesan;Aravindhan, S.
    • 통합자연과학논문집
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    • 제9권4호
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    • pp.261-267
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    • 2016
  • The crystal structure of the saliciline derivatives 4-chloro-2{[(2-hydroxy-5-methylphenyl)amino]methyl}5-methylphenol ($C_{15}H_{15}ClNO_2$) has been determined from single crystal X-ray diffraction data. In the title compound crystallizes in the monoclinic space group P21/c with unit cell dimension $a=11.5241(2){\AA}$, $b=8.733(2){\AA}$ and $c=13.649(2){\AA}$ [${\alpha}=90^{\circ}$, ${\beta}=130.876(2)^{\circ}$ and ${\gamma}=90^{\circ}$]. the title compound are essentially planar conformation. The compound lies across a crystallographic inversion centre and adopts E configurations with respect to the C-N bonds. The crystal packing of the molecules of compound is stabilized through weak O-H...O inter molecular interactions.

A Complexation Study of Novel Triaza and Hexaaza Macrocycles for the Use of Analytical Reagents

  • Wakita, Hisanobu;Yamaguchi, Toshio;Matsuki, Yuuichi;Kurisaki, Tsutomu
    • 분석과학
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    • 제8권4호
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    • pp.449-456
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    • 1995
  • Novel macrocyclic ligands modified with pendant arms, N, N', N'', N''', N'''', N'''''-hexakis(2-aminoethyl)-1, 4, 7, 10, 13, 16-hexaazacyclootadecane [$L_3$, Fig.1] and 1, 4, 7-tris(3-(o-hydroxyphenyl)propyl)-1, 4, 7-triazacyclononane [$L_4$, Fig.1] have been synthesized, and the protonation of $L_3$ and $L_4$ and stability constants of $L_3$ with bivalent transition metal ions and rare earth metal ions were determined by a potentiometry. The obtained results show that the complex formation of $L_3$ depends on the metal ligand ratios, and the stability of the metal complexes does not depend on the sizes of the metal ions, but on the nature of the metal ions. The structures of the rare earth complexes for $L_4$ were characterized by an X-ray absorption spectrometry(XAFS).

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