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

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An NMR Study of Solvent Interactions in a Paramagnetic System

  • Golding, R.M.;Pascual, R.O.;Suvanprakorn, C.;Dance, I.G.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1752-1756
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    • 2006
  • This study explores and interprets in a new way the complex solvent and the temperature dependence of the NMR shifts for the N-$CH_2$ protons in tris(N,N-diethyldithiocarbamato) iron(III) in acetone, benzene, carbon disulfide, chloroform, dimethylformamide and pyridine. The NMR shifts are interpreted in terms of the Fermi contact interaction and the dipolar term from the multipole expansion of the interaction of the electron orbital angular momentum and the electron spin dipolar-nuclear spin angular momentum. This analysis yields a direct measure of the effect of the solvent system on the environment of the transition metal ion. The results are analysed in terms of the crystal field environment of the transition metal ion with contributions from (a) the dithiocarbamate ligand (b) the solvent molecules and (c) the interaction of the effective dipole moment of the polar solvent molecule with the transition metal ion complex.

Studies on 1-Isonicotinoyl-2-furfurylidene hydrazine-Cu(II) Complex Compound. (1-Isonicotinoyl-2-furfurylidene Hydrazine-Cu(II) 착화합물에 관한 분석화학적연구)

  • 백남호;최윤수
    • YAKHAK HOEJI
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    • v.9 no.1_2
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    • pp.18-22
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    • 1965
  • A new organic reagent, 1-isonicotinoyl-2-furfurylidene hydrazine was synthesized from isonicotinic acid hydrazide and furfural, gives precipitate with copper(II), mercury(II) and argent(I), whereas, it gives a water soluble yellow complex with iron(III). Copper complex of the reagent is soluble in EtOH MtOH, pyridine, dioxane and dimethylformamide with green yellow coloration. The complex has a maximum absorption at 385 m.$\mu$ and molar ratio of copper; reagent was estimated as 1:1 by continuous variation method, slop method and chelate titration method. Molar extinction coefficient (9600) and apparant formation constant of this complex was spectrophotometrically determined. K=1.7 * $10^{7}$ (Babko's method) K=2.1 * $10^{7}$ (Anderson's method). This reagent reacted with copper so sensitive that it would be available for determination of Cu (II).

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Synthesis of Binuclear Bismacrocyclic Iron(II) Complex by the Aerobic Oxidation of Iron(II) Complex of 1,4,8,11-Tetraazacyclotetradecane

  • Myunghyun Paik Suh;Gee-Yeon Kong;Il-Soon Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.439-444
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    • 1993
  • The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

A New Porous Carbon via an Exfoliation of n-Octylammonium Tetrachloroferrate(III)-Graphite Intercalation Complex

  • 권채원;김동훈;최진호
    • Bulletin of the Korean Chemical Society
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    • v.19 no.10
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    • pp.1113-1116
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    • 1998
  • A new graphite intercalation compound (GIC), n-octylammonium tetrachlorofeffate(Ⅲ)-graphite, has been derived from well-known ferric chloride graphite intercalation compound. X-ray diffration study shows that the basal spacing of this new GIC is 20.8 Å. In order to investigate the local geometry around the iron atom in the graphite layers, X-ray absorption spectroscopy experiments were performed. The first discharge capacity of its exfoliated form is found to be 862 mAh/g, which is more than double the value of pristine graphite (384 mAh/g). Such a drastic increase implies that the exfoliated graphite is a promising electrode material.

Mineral Paragenesis and Fluid Inclusions of the Dongbo Tungsten-Molybdenum Deposits (동보(東寶) 중석(重石)-모리브덴 광상(鑛床)의 광물공생(鑛物共生)과 유체포유물(流體包有物))

  • Park, Hee-In;Moon, Sang Ho;Bea, Young Boo
    • Economic and Environmental Geology
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    • v.18 no.4
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    • pp.331-342
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    • 1985
  • The Dongbo tungsten-molybdenum deposits are fissure-filling veins emplaced in granites of late Cretaceous age. Integrated field, mineralogic and fluid inclusion studies were undertaken to illuminate the characters and origin of the ore deposits. Mineral paragenesis is complicated by repeated fracturing, but four distinct depositional stages can be recognized; (I) tungsten-molybdenum minerals-quartz-chlorite stage, (II) iron-oxide and sulfides-quartz stage, (III) iron -oxide-base metal sulfides-sulfosalts-quartz-carbonates stage, (IV) barren rhodochrosite-zeolite stage. Fluid inclusion studies were carried out for stage I quartz and stage III quartz, sphalerite and calcite. Fluid inclusion studies reveals highly systematic trends of homogenization temperature and salinity throughout the mineralization. Ore fluids during stage I were complex, NaCl rich brine and salinity reached values as high as 34.4 weight percent equivalent NaCl, but the later ore fluids were more dilute and reached to 9.7 weight percent equivalent NaCl during stage III. Intermittent boiling of ore fluid during stage I is indicated by the fluid inclusions in stage I quartz. Depositional temperatures and pressures during stage I range from $520^{\circ}C$ to $265^{\circ}C$and from 600 to 400 bars. Homogenization temperatures of the stage III quartz, sphalerite and calcite range from $305^{\circ}C$ to $190^{\circ}C$. Fluid inclusion data from the Dongbo mine are nearly similar to those from other hydrothermal tungsten deposits in the Kyeongsang basin. Depositional temperature and salinity of ore fluids during precipitation of tungsten-molybdenum minerals in Dongbo mine were much higher, but $CO_2$ contents were much lower than those from hydrothermal tungsten-molybdenum deposits of late Cretaceous plutonic association in central parts of Korean peninsula.

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A Study on Electronic Interaction in Dimetallic Complexes with Conjugated Chain (공액사슬로 연결된 이핵금속착체의 전자적 상호작용에 관한 연구)

  • Chung, Min-Chul;Munetaka Akita
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.17 no.6
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    • pp.652-660
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    • 2004
  • The cis-hex-3-ene-1,5-diynyl-bridged diiron compound 3, [(η$^{5}$ - $C_{5}$ M $e_{5}$ ) Fe(dppe)]$_2$($\mu$-C≡C-CH=CH-C≡C), have been prepared and characterized by cyclic voltammetry(CV), and electronic spectroscopy (UV-VIS and near-IR, NMR). From the results, compound 3 show two well resolved, single-electron, reversible oxidation waves by CV, and comproportionation constant(Kc) calculated from the CV data for compound 3. The Mixed-valence (MV) radical cation 3$^{+}$ show strong absorptions in the near IR, 1586 nm, and this band is more readily assigned as MV $\pi$-$\pi$ band of delocalized complex (Robin-Day Mixed-valence Class III), and the $H_{ab}$ , effective coupling parameter are most consistent with electronic delocalization.

Kinetic Studies on the Reaction of Iron (Ⅲ) with D-penicillamine in Acidic Solution$^1$

  • Hyun-Jae Park;Yung-Hee Oh Kim;Jung-Ae Shim;Sung-Nak Choi
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.444-449
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    • 1993
  • Anaerobic oxidation of D-penicillamine by Fe(III) in acidic solution has been studied kinetically by the use of stopped-flow system. The reaction is biphasic with a rapid complexation of 1: 1 complex, $Fepen^+$ (pen= D-penicillamine dianion) which is then internally reduced to Fe(II) and disulfide. Rates of both the complexation and the redox process are pH dependent and also are affected by the presence of chloride ion. Different from the reaction of Cu(II) with D-penicillamine, partially oxidized mixed-valence complex is not formed even transiently in this reaction.

Salmonella Typhimurium SL1344 Utilizing Human Transferrin-bound Iron as an Iron Source Regardless of Siderophore-mediated Uptake (Salmonella Typhimurium SL1344의 사람의 트렌스페린(hTf)에 부착된 철 이용에 관한 연구)

  • Choe, Yunjeong;Yoo, Ah Young;Kim, Sam Woong;Hwang, Jihwan;Kang, Ho Young
    • Journal of Life Science
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    • v.27 no.1
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    • pp.72-77
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    • 2017
  • Inorganic iron is essential for various metabolic processes, including RNA synthesis, electron transport, and oxygen detoxification in microorganisms. Many bacterial pathogens compete for iron acquisition in diverse environmental condition such as host. Salmonella Typhimurium SL1344 also requires inorganic iron as a cofactor for growth. When a M9 minimal liquid medium was supplemented with ethylenediamine di-o-hydroxyphenylactic acid (EDDA) which acts as an iron-chelating agent, growth of Salmonella Typhimurium SL1344 in the supplemented medium was completely arrested by deficient of useful iron under iron-depleted condition. However, a number of siderophores, which are small, high-affinity iron chelating compounds secreted by microorganisms such as bacteria and fungi, were produced for utilization of restricted iron under iron-depleted condition. A M9 minimal liquid medium complemented with human transferrin (hTf)-iron complex turned completely off production of siderophores, but growth of Salmonella Typhimurium SL1344 maintained level similar to compare one complemented with iron (III) chloride (FeCl3). This means that human transferrin (hTf)-bound iron can utilize via directly interaction with Salmonella Typhimurium SL1344 without productions of siderophores. Through construction and analysis of negative mutant for utilization of human transferrin (hTf)-bound iron, we confirm that the bacterium can directly use human transferrin (hTf)-bound iron without extracellularly intermediated carriers such as siderophores.

Complexation of Polyelectroyte-Metal(II) Ion. III. The Complex Formation of Iron(II), Cobalt(II), Nickel(II) and Copper(II) with Branched Poly(ethylene imine) (BPEI) in Aqueous Solution (Polyelectrolyte-Metal(II) 이온의 착물화 (제 3 보). Iron(II), Cobalt(II) Nickel(II) 및 Copper(II)와 Branched Poly(ethylene imine) (BPEI)간의 착물생성)

  • Dong Soo Kim;Tae Sub Cho
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.456-464
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    • 1986
  • The complex formation of branched poly(ethylene imine) (BPEI) with bivalent transition metal ions, such as Fe(II), Co(II), Ni(II) and Cu(II), have been investigated in terms of visible absorption and pH titration methods in an aqueous solution in 0.1M KCl at 30${\circ}$. The stability constants for M(II)-BPEI complexes was calculated with the modified Bjerrum method. The formation curves of M(II)-BPEI complexes showed that Fe(II), Co(II), Ni(II) and Cu(II) ions formed coordination compounds with four, two, two, and two ethylene imine group, respectively. In the case of Cu(II)-BPEI complex at pH 3.4 ∼ 3.8, ${\lambda}_{max}$ was shifted to the red region with a decrease in the acidity. The overall stability constants (log $K_2$) increased as the following order, Co(II) < Cu(II) < Ni(II) < Fe(II).

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