• Title/Summary/Keyword: Ligand-bridged

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Synthesis and Crystal Structures of Mn(II)- and Ni(II)-Dicarboxylate Complexes with 1,10-Phenanthroline

  • Koo, Bon-Kweon
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2299-2304
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    • 2012
  • Two new metal(II) complexes, $[Mn(dpa)(phen)(H_2O)_2]_n$ (1) ($H_2dpa$ = dephenic acid, phen = 1,10-phenanthroline) and $[Ni_2(nda)(phen)_2(H_2O)_6](nda)(H_2O)$ (2) ($H_2nda$ = 2,6-naphthalenedicarboxylic acid) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. In complex 1, Mn(II) ion is six-coordinated, and Mn(II) ions are bridged by dpa ligands into 1D chains. While, the complex 2 is dimer and two Ni(II) ions are bridged by one nda ligand cooperated with the terminal ligand phen. In each complex, the dicarboxylate ligand is coordinated to metal(II) ions as a bis-monodentate.

A Novel Al-Bridged Trinuclear Iron(II) Bis(imino)pyridyl Complex with Catalytic Ethylene Polymerization Behavior

  • Long, Zerong;Li, Zhongquan;Ma, Ning;Wu, Biao
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2537-2543
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    • 2011
  • A self-assembled Al-bridged diiminopyridine-based ligand (3) was synthesized and characterized by FT-IR, ESI-MS and NMR spectroscopy. Electron spectral titrations were performed to confirm the formation of a novel trinuclear bis(imino)pyridyl iron(II) complex (4) upon addition of $FeCl_2$ into Al-bridged ligand 3 in methanol solution. Simultaneously, a typical bis(imino)pyridine-iron(II) complex (2) was synthesized and fully characterized. The X-ray crystal study of the iron(II) complex 2 disclosed a five-coordinate, distorted square-pyramidal structure with the tridentate N^N^N ligand and chlorides. The optimal molecular structure of 4 was obtained by means of molecular mechanics, which showed that each iron atom in the complex 4 is surrounded by two chlorides, a tridentate N^N^N ligand and one oxygen atom, supporting considerations about the possibility of six-coordinate geometry from MMAO or the ethylene access. A comparison of 4 with the reference 2 revealed a remarkable decrease of the catalytic activity and MMAO consumption (activity up to $0.41{\times}10^3\;kg\;{mol_{Fe}}^{-1}h^{-1}bar^{-1}$, Al/Fe = 650 for 4 and $7.02{\times}10^3\;kg\;{mol_{Fe}}^{-1}h^{-1}bar^{-1}$, Al/Fe = 1600 for 2).

Vitamin B12 Model Complexes: Synthesis and Characterization of Thiocyanato Cobaloximes and Thiocyanato Bridged Dicobaloximes of O-donor Ligands: DNA Binding and Antimicrobial Activity (비타민 B12 모델 착물: O-주개 리간드인 Thiocyanato Cobaloximes 및 Thiocyanato로 연결된 Dicobaloximes의 합성 및 특성규명: DNA 결합 및 향균 활성)

  • Mustafa, Bakheit;Satyanarayana, S.
    • Journal of the Korean Chemical Society
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    • v.54 no.6
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    • pp.687-695
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    • 2010
  • Complexes of thiocyanato(L)cobaloximes where L is urea, acetamide, semicrabazide and formamide were synthesized and characterized. The reaction of thiocyanato (L) cobaloximes (SCNCo$(DH)_2$(L)) with benzyl (aquo) cobaloxime $PhCH_2Co(DH)_2(OH_2)$ was found to produce a series of thiocyanato bridged dicobaloximes of a general formula of $PhCH_2Co(DH)_2SCNCo(DH_2)(L)$. Evidence for formulation as dicobaloximes containing thiocyanato ligand bridges was obtained from infrared data which show $20-45cm^{-1}$ increase in vCN upon formation of the dicobaloxime from the corresponding terminal thiocyanocobaloxime (SCNCo$(DH)_2$(L)). Further characterization of these two series was done on the basis of ($^1H$,$^{13}C$)NMR, LCMS and elemental analysis. Anti-microbial activity of thiocyanato(L)cobaloximes and thiocyanato bridged dicobaloximes were screened against E. Coli. The DNA-binding behaviors of both monomers and dimers were investigated by spectroscopic methods and viscosity measurements. The results indicated that the dimer complexes bind with calf-thymus DNA in an intercalative mode via the terminal benzyl ring into the base pairs of DNA. It was observed that the monomer complexes did not interact with DNA. Fluorescence spectra for the interaction between thiocyanato bridged dicobaloximes and DNA were also studied.

Preparation of Dioxygen Bridged Palladium Complexes by Superoxide Ion $(O_2^-)$ (초과산화이온 $(O_2^-)$ 에 의한 산소가교팔라듐착화합물의 합성)

  • Pyeong Jin Chung
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.135-142
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    • 1984
  • New type dioxygen bridged complexes of palladium were prepared by using $KO_2$ as a source of superoxide ion $(O_2^-)$. The method is completely different from the traditional one which has adopted the oxidative addition of molecular oxygen to transition metal complexes in low valency. It was suggested that the reaction to prepare the dioxygen complexes proceeded via nucleophilic displacement followed by electron transfer reaction. Five new type dioxygen complexes having ${\pi}$-allyl ligand were prepared and characterized by the application of the reaction of $O_2^-$.

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Synthesis and Characteristics of Diphosphine-digold complexes as Light-Emitting Materials (발광 재료용 다이포스핀-다이골드 착물의 합성과 특성 연구)

  • Kim, Jun-Ho;Sohn, Byung-Chung;Ha, Yun-Kyoung
    • Journal of the Korean Applied Science and Technology
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    • v.19 no.2
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    • pp.103-107
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    • 2002
  • Diphosphine dinuclear gold(I) complexes were synthesized from the reaction of bridged diphosphines and gold ions. As a bridged diphosphine, 1,2-bis(diphenylphosphino)metbane (dppm) or 1,1'-Bis(diphenylphosphino) ferrocene (dppf) was introduced. As anionic ligands, CI was first coordinated to Au, resulting in (diphosphine)$(AuCl)_{2}$. Then, the ligand, SPh, was substituted for Cl in the chloride complex to give (diphosphine)$(AuSPh)_{2}$. As a result, three digold complexes, (dppm)$(AuCl)_{2}$. (I), (dppf)$(AuCl)_{2}$. (II), and (dppf)$(AuSPh_{2}$. (III) were prepared in this study. The thermal properties were investigated at first hand to confirm that the gold complexes were in fact formed. The digold complexes were decomposed above $200^{\circ}C$ while the ligand, dppm or dppf, melts under $180^{\circ}C$ The photoluminescence (PL) spectra of the spin-coated thin films showed the maximum peak at 590, 595, and 540nm for the complex, I, II, and III, respectively. These complexes were found to give the orange color phosphorescence. Therefore, these digold complexes can be candidates for orange-red phosphorescent materials in organic electroluminescent devices (OELD). Further studies on application of the complexes as a dopant in an emitting layer are in progress in our laboratory.

Syntheses of Polysiloxane-Bridged Dinuclear Metallocenes and Their Catalytic Activities

  • 노석균;김수찬;이동호;윤근병;이훈봉
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.618-622
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    • 1997
  • The polysiloxane-bridged dinuclear metallocenes $[(SiMe_2O)_n-SiMe_2(C_5H_4)_2][(C_9H_7)ZrCl_2]_2$ (n=1 (7), 2 (8), 3 (9)) have been generated as a model complex for the immobilized metallocene at silica surface by treating the respective disodium salts of the ligands with 2 equivalents of $(C_9H_7)ZrCl_3$ in THF. All three complexes are characterized by $^1H$ NMR and measurement of metal content through ICP-MS. It turned out that the values of ${\Delta}{\delta}=[{\delta}_d-{\delta}_p]$, the chemical shift difference between the distal $({\delta}_d)$ and proximal $({\delta}_p)$ protons, for the produced dinuclear compounds (0.47 for 7, 0.49 for 8, and 0.5 for 9) were larger than the Δδ value of the known ansa-type complex holding the same ligand as a chelating one, that is just the opposite to the normal trend. In order to compare polymerization behavior of the dinuclear metallocene with the corresponding mononuclear metallocene, (Cp)$(C_9H_7)ZrCl_2$ was separately prepared. To investigate the catalytic properties of the dinuclear complexes and mononuclear metallocenes ethylene polymerization has been conducted in the presence of MMAO. The polymerization results display the typical activity dependence on polymerization temperature for all complexes. The most important feature is that the polymers from the dinuclear metallocenes represent enormously improved molecular weight compared with the polymer from the corresponding mononuclear metallocene. In addition, the influence of the nature of the bridging ligand upon the reactivities of the dinuclear metallocenes has also been observed.