• Title/Summary/Keyword: Bridging Complex

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Synthesis and Crystal Structures of Zn(II)- and Mn(II)- Diphenyldicarboxylate Complexes with N-Donor Ligand

  • Koo, Bon Kweon
    • Journal of the Korean Chemical Society
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    • v.60 no.5
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    • pp.321-326
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    • 2016
  • Two new polymeric complexes, [Zn(dpa)(pyz)0.5]n (1; dpa = diphenate and pyz = pyrazine) and [Mn3(bpdc)3(py)4]n (2; bpdc = biphenyl-4,4'-dicarboxylate and py = pyridine) were successfully isolated by the hydro- and solvo-thermal technique, respectively. The complexes were characterized by elemental and thermal analysis, vibrational IR spectroscopy, and by single crystal x-ray structure determination. For 2, magnetic property was also investigated. Complex 1 is a two-dimensional layer structure consisting of a paddle-wheel building unit of Zn-dpa chains bridged by pyrazine. While, complex 2 consists of linear trimeric Mn3 cluster as building unit to form 3D network. In the complexes, dpa2− (1) and bpdc2−(2) ligands show a typical bis-monodendate bridging and two kinds of bridging modes; a typical bridging and chelating/bridging mode, respectively.

Electrophilic Attack of the Phenyl Isocyanate Carbon at the Bridging Imido Nitogen: Preparation and Structure of$ Mo_2({\mu-N(CONPh)Ph})({\mu-NPh)(NPh)_2(S_2CNEt_2)_2$

  • 김경;Lee, Soon W.
    • Bulletin of the Korean Chemical Society
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    • v.19 no.11
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    • pp.1211-1216
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    • 1998
  • Bis(diethyldithiocarbamato)ioxomolybdenum(VI), cis-MoO2(S2CNEt2)2, 1, reacted with chlorotrimethylsilane (Me33SiCl) to give a seven-coordinate, pentagonal bipyramidal complex MoOC12(S2CN]Et2)2, 3, in which the oxo ligand is trans to the chloride ligand and the two chloride ligands are mutually cis. The monooxo molybdenum complex bis(diethyidithiocarbamato)oxomolybdenum(IV), MoO(S2CNEt2)2, 2, reacted with phenyl isocyanate (PhNCO) to give an Mo dimer MO2{μ-N(CONPh)Ph}(μ-NPh)(NPh)2(S2CNEt2)2, 4, which contains an Mo-Mo bond, two diethyldithiocarbamato ligands, two terminal imido (NPh) ligands, and two bridging hnido (NPh) ligands. One of the two bridging NPh ligands seemed to have been attacked by the electrophilic phenyl isocyanate carbon, which suggests that the bridging imido NPh ligand is more nucleophilic than the terminal one. Crystallographic data for 3: monoclinic space group P21/c, a=8.908(l) Å, b=17.509(3) Å, c=12.683(2) Å, β=110.15(1)°, Z=4, R(wR2)=0.0611(0.1385). Crystallographic data for 4-THF: orthorhombic space group P212121, a=17.932(4) Å, b=22.715(5) Å, c=11.802(3) Å, Z=4, R(wR2)=0.0585(0.1286).

Sequence Dependent Binding Modes of the ΔΔ- and ΛΛ-binuclear Ru(II) Complexes to poly[d(G-C)2] and poly[d(A-T)2]

  • Chitrapriya, Nataraj;Kim, Raeyeong;Jang, Yoon Jung;Cho, Dae Won;Han, Sung Wook;Kim, Seog K.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2117-2124
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    • 2013
  • The binding properties and sequence selectivities of ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ (bip = 4,4'-biphenylene (imidazo [4,4-f][1,10]phenanthroline) complexes with $poly[d(A-T)_2]$ and $poly[d(G-C)_2]$ were investigated using conventional spectroscopic methods. When bound to $poly[d(A-T)_2]$, a large positive circular dichroism (CD) spectrum was induced in absorption region of the bridging moiety for both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes, which suggested that the bridging moiety sits in the minor groove of the polynucleotide. As luminescence intensity increased, decay times became longer and complexes were well-protected from the negatively charged iodide quencher compared to that in the absence of $poly[d(A-T)_2]$. These luminescence measurements indicated that Ru(II) enantiomers were in a less polar environment compared to that in water and supported by minor groove binding. An angle of $45^{\circ}$ between the molecular plane of the bridging moiety of the ${\Delta}{\Delta}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex and the local DNA helix axis calculated from reduced linear dichroism ($LD^r$) spectrum further supported the minor groove binding mode. In the case of ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex, this angle was $55^{\circ}$, suggesting a tilt of DNA stem near the binding site and bridging moiety sit in the minor groove of the $poly[d(A-T)_2]$. In contrast, neither ${\Delta}{\Delta}$-nor ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex produced significant CD or $LD^r$ signal in the absorption region of the bridging moiety. Luminescence measurements revealed that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes were partially accessible to the $I^-$ quencher. Furthermore, decay times became shorter when bis-Ru(II) complexes bound to $poly[d(G-C)_2]$. These observations suggest that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes bind at the surface of $poly[d(G-C)_2]$, probably electrostatically to phosphate group. The results indicate that ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ are able to discriminate between AT and GC base pairs.