• Title/Summary/Keyword: Binuclear

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Syntheses and Crystal Structures of Xylyl-Bridged NO2S2-Donor Macrocycles and Binuclear Mercury(II) Complex

  • Lee, Ji-Eun;Jin, Yong-ri;Seo, Joo-beom;Yoon, Il;Song, Mi-Ryoung;Lee, So-Young;Park, Ki-Min;Lee, Shim-Sung
    • Bulletin of the Korean Chemical Society
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    • v.27 no.2
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    • pp.203-207
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    • 2006
  • Isomeric series of dilinked $NO_2S_2$ macrocycles ($L^2$: para-, $L^3$: meta- and $L^4$: ortho-linked) capable of binuclear complexing ability were prepared from its monomeric analog $L^1$ in reasonable yields except ortho-type reaction, which led to mixture due to the formation of monomer-type macrocyclic quaternary ammonium bromide $L^5$. Moreover, L2 (as $2HNO_3$ form) and $L^5$ were confirmed by an X-ray crystallography. Reaction of $HgCl_2$ with $L^2$ yielded a binuclear complex $[Hg_2(L^2)Cl_4]$. In the complex, each mercury(II) has a distorted tetrahedral environment made up of S and N donors from an exodentate $L^2$ and two coordinated Cl atoms.

Oxygen Ring Formation Reaction of Monoxo-Bridged Binuclear Molybdenum (V) Complexes (I). Reaction of $[Mo_2O_3(bipy)_2(NCS)_4]$ with Solvent Water in Aqueous Acetone Mixture (한개의 산소다리를 가진 몰리브덴 (V) 착물의 산소고리화반응 (I). 아세톤 수용매에서 용매물과 $[Mo_2O_3(bipy)_2(NCS)_4]$ 의 반응)

  • Oh Sang Oh;Jin Ki Kwon;Chang Su Kim
    • Journal of the Korean Chemical Society
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    • v.30 no.4
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    • pp.345-351
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    • 1986
  • Monoxo-bridged binuclear molybdenum(V) complex, $[Mo_2O_3\;(bipy)_2\;(NCS)_4]$ in aqueous acetone mixture produces the corresponding dioxo-bridged binuclear molybdenum(V) complex, $MoO_4(bipy)_2(NCS)_2$. The rate of conversion of $[Mo_2O_3(bipy)_2(NCS)_4]$ to $MoO_4(bipy)_2(NCS)_2$ has been measured by spectrophotometric method. The rate of formation of dioxo-bridged binuclear molybdenum(V) complexes with solvent water follows the rate law, rate = k$[Mo_2O_3(bipy)_2(NCS)_4]\;[H_2O]$. The reaction mechanism for the formation of dioxo-bridged complex is discussed. The observed negative volume of activation shows that the complex is strongly attracted to the solvent molecules at transition state.

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Light-Induced Electron Transfer Reactions in FeⅡ-CoⅢ Binuclear Complexes ($Fe^{II}-Co^{III}$이핵착물의 광유발 전자이동반응)

  • Lee, Gyu Hwan
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.598-602
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    • 1994
  • Light-induced electron transfer reaction within binuclear complex $(NC)_5FeII-L-CoIII(NH_3)_5$ was studied with steady-state photolysis and the rate constants were measured for various bridging lignands. klight and quantum yields for BP, PHEN, DAP having conjugation between metal binding sites were about $3{\times}10^{-2} sec^{-1}$ and 1, and for BPEA having no conjugation were about $2{\times}10^{-4} sec^{-1}$ and 0.03. Light-induced electron transfer reaction within binuclear complex was proved to be the chemical mechanism which had charge transfer excited state MLCT*.

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1,4-Dicyanobutene Bridged Binuclear Iridium (I, III) Complexes and Their Catalytic Activities

  • Park, Hwa-Kun;Chin, Chong-Shik
    • Bulletin of the Korean Chemical Society
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    • v.8 no.3
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    • pp.185-189
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    • 1987
  • Reactions of $Ir(ClO)_4(CO)(PPh_3)_2$ with dicyano olefins, cis-NCCH = CH$CH_2$$CH_2$CN (cDC1B), trans-NCCH = CH$CH_2$$CH_2$CN (tDC1B), trans-NC$CH_2$CH = CH$CH_2$CN (tDC2B), and NC$CH_2$$CH_2$$CH_2$$CH_2$CN (DCB) produce binuclear dicationic iridium (I) complexes, $[(CO)(PPh_3)_2Ir-NC-A-CN-Ir(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (1a), tDC1B (1b), tDC2B (1c), DCB (1d)). Complexes 1a-1d react with hydrogen to give binuclear dicationic tetrahydrido iridium (Ⅲ ) complexes, $[(CO)(PPh_3)_2(H)_2Ir-NC-A-CN-Ir(H)_2(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (2a), tDC1B (2b), tDC2B (2c), DCB (2d)). Complexes 2a and 2b catalyze the hydrogenation of cDC1B and tDC1B, respectively to give DCB, while the complex 2c is catalytically active for the isomerization of tDC2B to give cDC1B and tDC1B and the hydrogenation of tDC2B to give DCB at $100^{\circ}C$.

Synthesis, Spectroscopic Studies of Binuclear Ruthenium(II) Carbonyl Thiosemicarba-zone Complexes Containing PPh3/AsPh3 as Co-ligands: DNA Binding/Cleavage

  • Sampath, K.;Sathiyaraj, S.;Jayabalakrishnan, C.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.367-373
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    • 2013
  • The ruthenium(II) ferrocenyl heterocyclic thiosemicarbazone complexes of the type $[RuCl(CO)(EPh_3)]_2L$ (where E = P/As; L = binucleating monobasic tridendate thiosemicarbazone ligand) have been investigated. Strutural features were determined by analytical and spectral techniques. Binding of these complexes with CT-DNA by absorption spectral study indicates that the ruthenium(II) complexes form adducts with DNA and has intrinsic binding constant in the range of $3.3{\times}10^4-1.2{\times}10^5M^{-1}$. The complexes exhibit a remarkable DNA cleavage activity with CT-DNA in the presence of hydrogen oxide and the cleavage activity depends on dosage.

Chemistry of Carbonate-Sulfur Flux

  • Q. Won Choi;Choi Han;Chang So-Young;Pyun Chong-Hong;Kim Chang-Hong
    • Bulletin of the Korean Chemical Society
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    • v.15 no.12
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    • pp.1118-1121
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    • 1994
  • Reactions of alkaline metal carbonates with sulfur are investigated in detail. The evolution of CO and a trace of $SO_2$ were observed in the course of reaction with major component of polysulfides. Some evidences that the reaction proceeds with breaking of terminal sulfur-sulfur bond in the sulfur polymer, and forming CO, $SO_2$ and polysulfide are presented. Polysulfides have the role of keeping free sulfur and allow it to react with other chemicals to rather high temperatures.plexes, whereas the binuclear and mononuclear complexes of Mn$^{2+}$ and Co$^{2+}$

Cyanide-Bridged CrIIIMnII Binuclear Complexes Based on [Mn(phen)2]2+ and Dicyanidechromate(III) Building Blocks: Syntheses, Crystal Structures, and Magnetic Properties

  • Li, Guo-Ling;Zhang, Li-Fang;Ni, Zhong-Hai;Kou, Hui-Zhong;Cui, Ai-Li
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1675-1680
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    • 2012
  • Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

Synthesis and Characterization of Homo Binuclear Macrocyclic Complexes of UO2(VI), Th(IV), ZrO(IV) and VO(IV) with Schiff-Bases Derived from Ethylene diamine/Orthophenylene Diamine, Benzilmonohydrazone and Acetyl Acetone

  • Mohapatra, R.K.;Ghosh, S.;Naik, P.;Mishra, S.K.;Mahapatra, A.;Dash, D.C.
    • Journal of the Korean Chemical Society
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    • v.56 no.1
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    • pp.62-67
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    • 2012
  • A series of homo binuclear complexs of the type $[M_2(L/L^')(NO_3)n].mH_2O$, [where $M=U{O_2}^{2+},\;Th^{4+},\;ZrO^{2+}$] and $[(VO)_2(L/L^')(SO_4)_2]{\cdot}2H_2O$, L=1,5,6,9,12,15,16,20 octaaza-7,813,14-tetraphenyl-2,4,17,19-tetramethyl-1,4,6,8,12,14,16,19-docosaoctene (OTTDO) or L'=10:11;21:22-dibenzo-1,5,6,9,12,15,16,20-octaaza-7,813,14-tetraphenyl-2,4,17,19-tetramethyl-1,4,6,8,12,14,16,19-docosaoctene (DOTTOT), n=4 for $U{O_2}^{2+}$, $ZrO^{2+}$ n=8 for $Th^{4+}$ m=1,2,3 respectively, have been synthesized in template method from ethylenediamine/orthophenylene diamine, benzil monohydrazone and acetyl acetone and characterized on the basis of elemental analysis, thermal analysis, molar conductivity, magnetic moment, electronic, infrared, $^1H$-NMR studies. The results indicate that the VO(IV) ion is penta co-ordinated yielding paramagnetic complexes; $UO_2(VI)$, ZrO(IV) ions are hexa co-ordinated where as Th(IV) ion is octa co-ordinated yielding diamagnetic complexes of above composition. The fungi toxicity of the ZrO(IV) and VO(IV) complexes against some fungal pathogen has been studied.

New Unsymmetric Dinuclear Copper(II) Complexes of Trans-disubstituted Cyclam Derivatives: Spectral, Electrochemical, Magnetic, Catalytic, Antimicrobial, DNA Binding and Cleavage Studies

  • Prabu, R.;Vijayaraj, A.;Suresh, R.;Jagadish, L.;Kaviyarasan, V.;Narayanan, V.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1669-1678
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    • 2011
  • Six new binuclear copper(II) complexes have been prepared by template condensation of the dialdehydes 1,8-[bis(3-formyl-2-hydroxy-5-methyl)benzyl]-l,4,8,11-tetraazacyclotetradecane (PC-a) and 1,8-[bis(3-formyl-2-hydroxy-5-bromo)benzyl]-l,4,8,11-tetraazacyclotetradecane (PC-b) with appropriate aliphatic diamines, and copper(II) perchlorate. The structural features of the complexes have been confirmed by elemental analysis, IR, UV-vis and mass spectra etc. The electrochemical behavior of all the copper(II) complexes show two irreversible one electron reduction process. The room temperature magnetic moment studies depict the presence of an antiferromagnetic interaction in the binuclear complexes. The catechol oxidation and hydrolysis of 4-nitrophenylphosphate were carried out by using the complexes as catalyst. The antimicrobial screening data show good results. The binding of the complexes to calf thymus DNA (CT DNA) has been investigated with absorption and emission spectroscopy. The complex [$Cu_2L^{1a}$] displays significant cleavage property of circular plasmid pBR322 DNA in to linear form. Spectral, electrochemical, magnetic and catalytic studies support the distortion of the copper ion geometry that arises as the macrocyclic ring size increases.