• Title/Summary/Keyword: Tetranuclear

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Catalytic Hydrolysis of Phosphate Diesters as DNA Model with Tetranuclear Nickle (II) Complex

  • Sung, Nack-Do;Kim, Tae-Young
    • Journal of Applied Biological Chemistry
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    • v.49 no.3
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    • pp.86-89
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    • 2006
  • The novel tetranuclear nickel (II) complex is a high rate accelerator in promoting hydrolysis of phosphate diesters. Nickel-bound bis-nitrophenyl phosphate (BNPP) can be $10^4$ times more reactive than the unbound BNPP. The large rate of enhancements by the complex slightly under basic condition has shown high catalytic activity in phosphate diester cleavage. The bell-shaped pH-rate profile indicated that the nickel-oxide form of the tetranuclear complex or its kinetic equivalent was the active species for cleaving BNPP. The catalytic hydrolysis between tetranuclear nickel (II) complex and phosphate diester proceeds via the formation of bidentate coordination of the anionic phosphate to the Ni (II) atom. This reveals that the complex has the possibility as artificial nuclease.

Hydrothermal Synthesis, Crystal Structure and EPR Property of Tetranuclear Copper(II) Cluster [Cu4OCl6(C14H12N2)4]

  • Jian, Fang-Fang;Zhao, Pu-Su;Wang, Huan-Xiang;Lu, Lu-De
    • Bulletin of the Korean Chemical Society
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    • v.25 no.5
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    • pp.673-675
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    • 2004
  • The tetranuclear copper(II) cluster compound $[Cu_4OCl_6(C_{14}H_{12}N_2)_4]$ has been synthesized by hydrothermal reaction and studied by X-ray diffraction. The four copper(II) atoms locate four capsheaves of a tetrahedral skeletal structure and a oxygen atom as interstitial atom occupies the center position of the same tetrahedron, and each edge of the Cu-Cu tetrahedron is bridged by one ${\mu}_2$-Cl anion. The copper atom possesses slightly distorted trigonal bipyramidal geometry with three ${\mu}_2$-Cl atoms in equatorial position and the interstitial O atom and one N atom from 3-benzyl-benzimidazole ligand occupying axial position. The Cu-Cu distances are in the range of 3.0986-3.1162 ${\AA}$. The EPR spectrum suggested that the copper(II) ground state $d_{x2-y2}$ and the coordination geometry was trigonal bipyramidal.

A New Adamantane-like Tetranuclear Manganese(III) Complex Based on Flexible Schiff-base Ligand: Synthesis, Crystal Structure and Magnetic Property

  • Zhang, Ran;Ni, Zhong-Hai;Zhang, Li-Fang;Kou, Hui-Zhong
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.1965-1969
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    • 2014
  • A new tetranuclear Mn(III) complex $[Mn^{III}{_4}(sae)_4({\mu}_3-O)({\mu}_{1,1}-N_3)(OH)(H_2O)_2]{\cdot}H_2O$ (1) ($H_2sae$ = 2-salicylideneamino-1-ethanol) has been synthesized by the reaction of $MnCl_2{\cdot}4H_2O$, $H_2sae$ and sodium azide in the mixed solvent of methanol, acetonitrile and water. The X-ray diffraction analysis shows that the four Mn(III) ions in complex 1 have a unique adamantine arrangement, whereas the coordination environment of each Mn(III) ions is different. Magnetic studies indicate that complex 1 manifests antiferromagnetic behaviors. The magnetic susceptibilities of complex 1 have been fitted by two magnetic models based on the suitable analysis of its magnetic structural topology.

Crystal Packing of Two Different Tetranuclear Iron(III) Clusters, [(tacn)4Fe4O2(OH)4]2.8Br.9H2O (tacn = 1,4,7-triazacyclononane)

  • Jin, Mi-Kyung;Kim, Yoo-Jin;Jung, Duk-Young;Heu, Min;Yoon, Seok-Won;Suh, Byoung-Jin
    • Bulletin of the Korean Chemical Society
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    • v.26 no.2
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    • pp.253-259
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    • 2005
  • [$(tacn)_4Fe_4O_2(OH)_4]_2{\cdot}8Br{\cdot}9H_2O$ (tacn = 1,4,7-triazacyclononane), a tetranuclear iron(III) complex was synthesized by the hydrolysis of (tacn)FeCl3 and crystallizes in the orthorhombic space group, Pca2(1), with cell parameters, a = 37.574(3) $\AA$, b = 16.9245(12) $\AA$, c = 14.2830(11) $\AA$, V = 9082.9(12) ${\AA}^3$. [$(tacn)_4Fe_4O_2(OH)_4]^{4+}$ cations approach S4 point symmetry containing an adamantane skeleton. Four Fe(III) atoms have distorted octahedral environments with two hydroxo and an oxo bridges. Two [$(tacn)_4Fe_4O_2(OH)_4]^{4+}$ clusters having different Fe…Fe distances are connected to each other by the networked hydrogen bonds. The electrochemical behavior reveals irreversible three cathodic and two anodic peaks. Magnetic properties are characterized by antiferromagnetic (AF) interactions between Fe(III) ion spins. However, the low-lying states are still magnetic and exhibit a blocking behavior and a magnetic hysteresis at low temperatures.

Solution Dynamics and Crystal Structure of $CpMoOs_{3}(CO)_{10}(\mu-H)_{2}[\mu_{3}-\eta^{2}-C(O)CH_{2}Tol]$

  • Joon T. Park;Jeong-Ju Cho;Kang-Moon Chun;Sock-Sung Yun;Kim SangSoo
    • Bulletin of the Korean Chemical Society
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    • v.14 no.1
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    • pp.137-143
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    • 1993
  • The tetranuclear heterometallic complex CpMo$Os_3(CO)_{10}({\mu]-H)2[{\mu}3-{\eta}^2-C(O)CH_2Tol]\;(1,\;Cp={\eta}^5-C_5H_5,\;Tol=p-C_6H_4Me)$ has been examined by variable-temperature $^{13}$C-NMR spectroscopy and by a full three-dimensional X-ray structual analysis. Complex 1 crystallizes in the orthorhombic space group Pna2$_1$ with a = 12.960(1) ${\AA}$, b = 11.255(l) ${\AA}$, c = 38.569(10)${\AA}$, V = 5626(2) ${\AA}^3$ and ${\rho}$(calcd) = 2.71 gcm$^{-3}$ for Z = 8 and molecular weight 1146.9. Diffraction data were collectedon a CAD4 diffractometer, and the structure was refined to $R_F$ = 9.7% and $R_{W^F}$ = 9.9% for 2530 data (MoK${\alpha}$ radiation). There are two essentially equivalent molecules in the crystallographic asymmetric unit. The tetranuclear molecule contains a triangulated rhomboidal arrangement of metal atoms with Os(2) and Mo at the two bridgehead positions. The metal framework is planar; the dihedral angle between Os(l)-Os(2)-Mo and Os(3)-Os(2)-Mo planes is 180$^{\circ}$. A triply bridging (${\mu}_3,\;{\eta}^2$) acyl ligand lies above the Os(l)-Os(2)-Mo plane; the oxygen atom spans the two bridgehead positions, while the carbon atom spans one bridgehead position and an acute apical position. The molecular architecture is completed by an ${\eta}^5$-cyclopentadienyl ligand and a semi-triply bridging carbonyl ligand on the molybdenum atom, and nine terminal carbonyl ligands-four on Os(3), three on Os(l), and two on Os(2). The two hydride ligands are inferred to occupy the Os(l)-Os(2) and Mo-Os(3) edges from structural and NMR data.

Synthesis and Characterization of Tetranuclear Molybdenum(Ⅵ) Complexes with Butylamidoxime Derivatives (부틸아미드옥심 유도체의 몰리브덴(Ⅵ) 사핵 착물의 합성과 성질)

  • Roh, Soo-Gyun;Oh, Sang Oh
    • Journal of the Korean Chemical Society
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    • v.39 no.7
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    • pp.552-558
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    • 1995
  • The tetranuclear complexes, $X_2[M_{O4}O_12{R'C(NH_2)NO}_2](X= n-Bu_4N^+$, $R'=(CH_3)_2CH$, $CH_3CH_2CH_2$, $CH_3SCH_2$; $X=(CH_3)_2CHC(=NH_2)NH_2^+$, $R'=(CH_3)_2CH$; $X = CH_3CH_2CH_2C(=NH_2)NH_2^+$, $R'=CH_3_CH_2CH_2$; $X=CH_3SCH_2C(=NH_2)NH_2^+$, $R'=CH_3SCH_2)$ have been synthesized by the reactions of monomeric and polynuclear complexes with isobutyl-, butyl- and thiomethylacetamidoxime. The prepared complexes were identified by elemental analysis, infrared, $^1H$ NMR and $^{13}C$ NMR spectroscopy. The structure of complex ${(CH_3)_2CHC(NH_2)_2}_2[M_{O4}O_{12}{(CH_3)_2CHC(NH_2)NO}_2]$ was determined by X-ray single crystal diffraction. Crystal data are follows: Monoclinic, $P2_{1/c}$, $a=10.168(3){\AA}$, $b=11.768(1){\AA}$, $c=13.557(1){\AA}$, ${\beta}=102.08(1)^{\circ}$, $V=1586.2(5){\AA}^3$, Z=2, final R=0.026 for 2951($F_0>3s(F_0)$). This complex is composed of a planar cyclic $[Mo_4({\mu}-O)_4]$ and two ${\mu}_4$-amidoximate.

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