• Title/Summary/Keyword: 배위

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Magnetic and Infrared Spectral Studies of Oxovanadium (IV)-Carboxylate Complexes (옥소바나듐 (IV)-카르복실레이트 착물의 자기적 및 적외적 분광학적 성질)

  • Yoon-Bo Shim;Sung-Nak Choi;Jong-Yul Park
    • Journal of the Korean Chemical Society
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    • v.30 no.1
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    • pp.76-83
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    • 1986
  • Four oxovandium(IV) complexes with carboxylate ligands, $VO(picn)_2$, $VO(htmq)_2$, $VO(quin)_2$ and $VO(pyra)_2{\cdot}2H_2O)$ have been prepared and studied. Infrared spectral data coupled with the results of magnetic susceptibility study strongly suggest that there are relatively strong intermolecular interactions in $VO(picn)_2$ and $VO(htmq)_2$. In all oxovanadium(IV) complexes studied in this work, the carboxylate ligand coordinates to the metal ion in the unidentated fashion. Some fundamental vibration modes of oxovanadium(IV) complexes were empirically assigned from the difference in the spectrum of metal complex with free ligand.

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Studies on the oxygen-Atom-Transfer Reactions of Peroxo Vanadium(Ⅴ) Complexes (Peroxo Vanadium(Ⅴ)화합물들에 의한 산소 원자 전이 반응에 관한 연구)

  • Won, Tae Jin
    • Journal of the Korean Chemical Society
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    • v.45 no.3
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    • pp.213-218
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    • 2001
  • The reaction of peroxo vanadium(V) complexes, $VO(O_2)_2(pic)^{2-}$, $VO(O_2)(nta)^{2-}$, and $VO(O_2)(dipic)^-$ with thiolato-cobalt(III), $(en)_2Co(SCH_2CH_2NH_2)^{2+}$ resulted in an oxygen-atom transfer in aqueous solutions. Rate constants ($M^{-1}S^{-1}$) for these reactions were (35$\pm$1), $(4.8{\pm}0.4){\times}10^{-2}$ , and $(8.6{\pm}0.5){\times}10^{-4}$, respectively. The coordinate peroxide was activated in the oxygen-atom-transfer reaction of $VO(O_2)_2(pic)^{2-}$, but it is not the case for VO(O$_2$) $(nta)^{2-}$ and VO(O$_2$) $(dipic)^-$. In this paper, we proposed that the direct attack of an electrophilic peroxide to a nucleophilic substrate occurs in the oxygen-atom transfer pathway of peroxo vanadium(V) complexes.

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Two-dimensional Zinc Coordination Polymer Based Paddle-Wheel Type Secondary Building Units of $Zn_2(CO_2R)_4$: [Zn(ATP)(DMF)] $(ATP=2-aminoterephthalate,\;H_2N-C_6H_3-1,4-(COO)_2;\;DMF\;=\;N,\;N-dimethylformamide)$ (Paddle-wheel유형의 2차 쌓음 단위 $Zn_2(CO_2R)_4$에 기초한 2차원 아연 배위 고분자: [Zn(ATP)(DMF)] $(ATP=2-aminoterephthalate,\;H_2N-C_6H_3-1,4-(COO)_2;\;DMF\;=\;N,\;N-dimethylformamide)$)

  • Min Dongwon;Lee Hee K.;Lee Soon W.
    • Korean Journal of Crystallography
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    • v.15 no.2
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    • pp.78-82
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    • 2004
  • The solvothermal reaction of zinc(H) nitrate $(Zn(NO_3)_2\;{\cdot}\;6H_2O)$ with $ATP(2-aminoterephthalate,\;H_2N-C_6H_3-1,4-(COO)_2)$ in a mixture of solvents of DMF and ethanol, in the presence of benzene, gave a 2 dimensional zinc polymer [Zn(ATP) (DMF)] (1). X-ray structure determination revealed that two zinc metals and four ATP ligands form the paddle-wheel SBUs, which are linked by the ATP ligands to give a 2-D square-grid network. Each square grid has approximate dimensions of $11.1\times11.1\;{\AA}$ based on Zn metals. Benzene was required to produce high-quality crystals of polymer 1.

Behavior of Rare Earth Elements in Synthetic Fluorapatites Revealed by Rietveld Structure Refinement Data (리트벨트법에 의한 합성인회석 내의 희토류 원소의 거동에 관한 연구)

  • 문용희;최진범;이병임
    • Journal of the Mineralogical Society of Korea
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    • v.13 no.4
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    • pp.221-230
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    • 2000
  • 이성분 희토류 원소로 치환된 4종류의 합성불화인회석(synthetic fluorapatite) (Ap49: La+Gd, Ap50:Ce+Dy, Ap51: Pr+Er, Ap54: Eu+Lu; $Ca{10-x-2y}$ $Na_{y}$ $REE_{x+y}$($P_{1-x}$ //$Si_{x}$ $_{4}$)$_{6}$ $F_{2}$, x=0.13~0.12, y=0.26~0.42)을 대상으로 X-선 회절분석을 통해 얻어진 자료를 이용하여 리트벨트 구조분석을 실시하고 치환된 희토류원소의 거동을 단결정법으로 구해진 결과와 비교.분석하였다. 리트벨트 구조분석결과 합성불화인회석은 공간군 $P6_3$/m, 단위포는 평균하여 a=9.3906(1) $\AA$, c=6.8924(1) $\AA$, V=527.36 $\AA^3$의 값을 갖는다. 구조의 정밀도를 나타내는 R 지수를 보면 $R_{B}$ / 값은 17.29~18.80이고 S(GofF)값은 1.44~1.68로 계산되었다. 불화인회석은 9개의 산소를 배위하는 Ca1자리와 6개의 산소와 하나의 불소가 배위하는 Ca2자리가 있으며 Ca1-O의 평균거리는 2.563 $\AA$이고 Ca2-O의 평균거리는 $2.460 \AA$으로 Ca1자리가 Ca2자리보다 다소 크다. 구조자리 치환식에서는 $Ca^{2+}$ / 자리를 치환하는 $REE^{3+ }$ 로 인하여 전하균형을 맞춰주기 위해서 인과규소가 함께 참여하였다. ($REE^{3}$+Si$^{ 4+}$ $2Ca^{2+}$ : Ca1) 계산된 희토류원소의 자리점유율(REE-Ca2/REE-Cal)은 원자번호가 증가함에 따라 일정하게 감소하는 경향을 보여주며 이는 희토류원소의 거동이 LREE는 크기가 상대적으로 작은 Ca2 자리에 우선 치환되고 HREE는 크기가 큰 Ca1자리에 우선 치환되는 경향을 지시한다.

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Ruthenium Catalyzed Synthesis of N-Substituted Perhydroazepine Derivatives (루테늄 촉매를 이용한 N-치환 과수소아제핀 유도체의 합성)

  • Sim, Sang Cheol;Do, Chil Hun;Lee, Seung Yeop;Jo, Wan Ho;Heo, Geun Tae
    • Journal of the Korean Chemical Society
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    • v.34 no.6
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    • pp.652-657
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    • 1990
  • Primary amines react with 1,6-hexanediol at 180$^{\circ}C$ for 5 h under argon atmosphere in the presence of both $RuCl_3{\cdot}3H_2$O and $PR_3$ to give N-substituted perhydroazepine derivatives in good yields. For aromatic amines such as anilines, $RuCl_3{\cdot}3H_2$O combined with $PPh_3$ showed the highest catalytic activity. On the other hand, in the reaction of aliphatic amines, $RuCl_3{\cdot}3H_2$O combined with $PBu_3$ showed the highest catalytic activity. These differences may be attributed to the difference in the basicity of these amines. Less basic aromatic amines may require less basic phosphines, while more basic aliphatic amines may require more basic phosphines as the ligands.

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Structural Studies on Complexes of Substituted B15C5 with Nd(Ⅲ) (Nd(Ⅲ)과 B15C5 치환체와의 착물의 구조에 관한 연구)

  • Kim, Hae-Joong;Shin, Young-Kook;Kim, Si-Joong
    • Journal of the Korean Chemical Society
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    • v.39 no.9
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    • pp.692-697
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    • 1995
  • The chemical compositions and possible structure for the complex of B15C5 with Nd(Ⅲ) have been determined by NMR spectrophotometry in acetone-d6. On the stepwise additions of Nd(Ⅲ) to B15C5 solution of constant concentration, all the resonances shifted to downfield and the mole ratio of B15C5 to Nd(Ⅲ) was found to be 1 : 1. From the line broadening of proton peaks of NMR spectra, it was found that oxygen atoms in B15C5 interact with Nd(Ⅲ) ion. And in IR spectra of Nd(Ⅲ)-B15C5 complex, the band of asymmetric C-C-O stretching vibration shifted to a lower frequency region upon complexation. We have proposed the possible structure of the Nd(Ⅲ)-B15C5 coordinated with the five ether oxygen atoms and with the three bidentate nitrato groups.

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Solvent Mediated Hydrogen-bonded Supramolecular Network of a Cu(II) Complex Involving N2O Donor Ligand and Terephthalate (N2O 주개 리간드와 테레프탈레이트를 포함하는 구리(II) 착물의 용매를 매개로 한 수소결합형 초분자 네트워크)

  • Chakraborty, Jishnunil
    • Journal of the Korean Chemical Society
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    • v.55 no.2
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    • pp.199-203
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    • 2011
  • The title one-dimensional hydrogen-bonded coordination compound $[Cu^{II}(C_{13}H_{17}N_3OBr)(C_8H_5O_4)]{\cdot}2H_2O.CH_3OH$ has been synthesized and characterized by single crystal X-ray diffraction study. The monomeric unit contains a square-planar $Cu^{II}$ centre. The four coordination sites are occupied by a tridentate anionic Schiff base ligand (4-bromo-2-[(2-piperazin-1-yl-ethylimino)-methyl]-phenol) which furnishes an $N_2O$-donor set, with the fourth position being occupied by the oxygen atom of an adjacent terephthalate unit. Two adjacent neutral molecules are linked through intermolecular N-H---O and O-H---N hydrogen bonds and generate a dimeric pair. Each dimeric pair is connected with each other via discrete water and methanol molecules by hydrogen bonding to form a one-dimensional supramolecular network.

A $M\"{o}ssbauer$ Spectroscopic Sthdy of Ion Distribution in $Ba_{2}{(Co,Zn)}_{2}Fe_{12}O_{22}$ ($M\"{o}ssbauer$ 분광 분석에 의한 $Ba_{2}{(Co,Zn)}_{2}Fe_{12}O_{22}$ 내의 이온 분포 연구)

  • 최상준;권순주
    • Journal of the Korean Magnetics Society
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    • v.6 no.2
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    • pp.73-79
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    • 1996
  • Y-type hexagonal ferrites$(Ba_{2}Me_{2}Fe_{12}O_{22}:Me=transition metal)$ have promising electromagnetic properties in GHz range. Co and Zn are good candidates for the transition metal. To understand their role on the properties, it is thus necessary to study the ion(s) distribution in that complex Y-type hexagonal ferrite structure. The authors report Mossbauer spectroscopic results from very reliable samples, which has been extensively characterized by chemical analysis, Rietveld analysis of X-ray diffraction patterns, and magnetic property measurements. Analyzing two samples, $Co_{2}Y$ and $Co_{1.6}Zn_{0.4}Y$, conclusions are made as follow: (1) Co ions prefer the tetrahedral interstitial sites in the S-block $(6c_{IV})$ and the octahedral sites $(18h_{VI})$ at the interface of S- and T-block. (2) Partial substitution of Co with Zn (within the experimental range) does not disturb the Fe distribution.

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Carbonylative Cyclization of Unsaturated Carboxylic Acids by Palladium Complexes with Phosphines(I) Synthesis and Structure of Palladium(O, II) Complexes with Unsaturated Carboxylic Acids (포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화고리 반응 (제 1 보). 불포화카르복실산이 배위된 팔라듐(0, Ⅱ) 착물의 합성과 구조)

  • Myung-Ki Doh;Maeng-Jun Jung;Dong-Jin Lee;Kohtaro Osakada;Akio Yamamoto
    • Journal of the Korean Chemical Society
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    • v.37 no.4
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    • pp.423-430
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    • 1993
  • New Palladium(0)-olefin complexes, $(PMe_3)_2Pd{CH_2=C(CH_3)COOH} \;and\;(PMe_3)_2Pd{(CH_3)CH=CHCOOH}$ have been prepared by treating $Pd(PMe_3)_2$(styrene) with methacrylic acid and trans-crotonic acid, respectively. These complexes were characterized by elemental analysis, IR and $^1H-,\;^{13}C-,\;and\;^{31}P$-NMR spectroscopy. The carboxylic acid entity was found non-bonded with palladium while ${\pi}$-bond is formed between the olefin double bond and Pd(0). The results are compared with the metallacycle formation the reaction of Pd(PMe3)2(styrene) with 3-butenoic acid.

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Synthesis and Characterization of a Novel Organotin Complex: Di(n-butyl) chloro[5-(p-dimethylaminobenzylidene)rhodanine]tin(IV) Based on a Competing N, O, and S Donor Ligand (새로운 유기주석 착물의 합성과 특성: 경쟁적인 N, O 및 S 주개 리간드에 기초한 Di(n-butyl)chloro[5-( p-dimethylaminobenzylidene)rhodanine]tin(IV))

  • Tarassoli, Abbas;Sedaghat, Tahereh;Mousavi, Fatemeh
    • Journal of the Korean Chemical Society
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    • v.55 no.4
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    • pp.590-593
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    • 2011
  • A novel organotin(IV) complex has been prepared from $Bu_2SnCl_2$ and the N, O and S donor ligand, 5-(p-dimethylaminobenzylidene) rodanine (HL). The ligand is deprotonated in the presence of a base and the complex with the general formula $SnBuCl_2L$ is formed. This complex was fully characterized by IR, $^1H$ NMR and $^{119}Sn$ NMR and elemental analysis. Spectroscopic data indicate the ligand is coordinated through the oxygen atom to the tin and the coordination number of four is supported by $^{119}Sn$ NMR data in solution.