• Title/Summary/Keyword: Coordination chemistry

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Synthesis, Structures and Properties of Three Metal-organic Frameworks Based on 3-(4-((1H-imidazol-1-yl)methyl)phenyl)acrylic Acid

  • Liang, Peng;Ren, Tian-Tian;Tian, Wei-Man;Xu, Wen-Jia;Pan, Gang-Hong;Yin, Xian-Hong
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.182-188
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    • 2014
  • Three new transition metal complexes based on Ozagrel $[Cu(Ozagrel)]_n$ (1), $[Zn(Ozagrel)(Cl)]_n$ (2), ${[Mn_2-(Ozagrel)(1,4-ndc)_2]{\cdot}(H_2O)}_n$ (3), (Ozagrel = 3-(4-((1H-imidazol-1-yl)methyl)phenyl)acrylic acid; 1,4-ndc = 1,4-Naphthalenedicarboxylic acid) have been hydrothermally synthesized and characterized by elemental analyse, IR, TG, PXRD, electrochemical analysis and single crystal X-ray diffraction. X-ray structure analysis reveals that 1 and 3 are 3D coordination polymers, while complex 2 is a two-dimensional network polymer, the 2D layers are further packed into 3D supramolecular architectures that are connected through hydrogen bonds. The electrochemistry of 1-3 was studied by cyclic voltammetry in methanol and water using a glassy carbon working electrode. Also, thermal decomposition process and powder X-ray diffraction of complexes were investigated.

Solution Nuclear Magnetic Resonance Spectral Characterization of Iron(II) Porphyrin Complexes of Weakly Coordinating Anions

  • Song, Byung-Ho;Park, Bong-Jin;Han, Chul-Hee
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.119-122
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    • 2002
  • Weakly coordinating anions show little affinity for binding to unfunctionalized iron(II) porphyrins. The electron-deficient 5, 10, 15, 20-tetrakis(pentafluorophenyl)porphinatoiron(II) compound is utilized in this study to demonstrate solution coordination by chloride, bromide and acetate ions. The binding strength of anions to the iron(II) porphyrin is reflected by a systematic change in pyrrole proton chemical shift in $^1H$ NMR spectra; the pyrrole resonance moves downfield when the ${\sigma}$-donor ability of anions is decreased.

Enantioselective Hydrosilylation of Imines Catalyzed by Diamine-Zinc Complexes

  • Park, Bu-Mahn;Feng, Xinhui;Yun, Jae-Sook
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.2960-2964
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    • 2011
  • The efficient asymmetric hydrosilylation of imines in the presence of polymethylhydrosiloxane has been investigated by screening chiral diamine-zinc complexes. A series of chiral diamine ligands were prepared from optically pure 1,2-diphenyl-1,2-ethanediamine and screened for effectiveness. N-Benzylic substituents were required for high enantioselectivity; ligands with bulky groups or extra coordinating groups such as OH and S lowered the catalytic activity. The level of asymmetric induction was usually in >90% ee range for aromatic imine substrates. A linear correlation between the ee of the ligand and that of the product was observed, indicating the presence of a 1:1 ratio of ligand to metal coordination in the active catalytic complex.

N3S-ligated Copper(II) Complex Catalyzed Selective Oxidation of Benzylic Alcohols to Aldehydes under Mild Reaction Conditions

  • Dharmalingam, Sivanesan;Koo, Eunhae;Yoon, Sungho;Park, Gyoosoon
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.715-720
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    • 2014
  • A Cu(II) complex with an three nitrogens and one sulfur coordination environment was synthesized and characterized. Its redox potential was observed at 0.483 V vs. NHE, very similar to that of a Cu-containing fungal enzyme, galactose oxidase, which catalyzes the oxidation of alcohols to corresponding aldehydes with the concomitant reduction of molecular oxygen to water. The Cu(II) complex selectively oxidizes the benzylic alcohols using TEMPO/$O_2$ under mild reaction conditions to corresponding aldehydes without forming any over-oxidation product. Moreover, the catalyst can be recovered and reused multiple times for further oxidation reactions, thus minimizing the waste generation.

Manganese Metallamacrocycles with Various Coordination Solvents

  • Song, Ji-Heh;Moon, Doh-Yun;Lah, Myoung-Soo
    • Bulletin of the Korean Chemical Society
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    • v.23 no.5
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    • pp.708-714
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    • 2002
  • The hexanuclear metallamacrocycles were observed repeatedly in various conditions including the presence of several different tricationic metal ions in the macrocyclic ring system and of the linear alkyl chains at the acyl site of N-acylsalicylhydrazide ligand, which contrasts to the formation of the decanuclear metallamacrocycle with bulkier side chains such as phenyl group at the acyl site of the ligand. We synthesized a series of metallamacrocycles in various solvents to find the relationship between the solvents and the nuclearity of the metallamacrocycles. Whether the solvents are sterically more demanding or not, the complexes formed kept the hexanuclear metallamacrocycle system.

Structures and Sorption Properties of 2-Methylbenzimidazolate-Based Zn(II) Frameworks

  • Phang, Won Ju;Lee, Woo Ram;Hong, Chang Seop
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2419-2422
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    • 2014
  • The syntheses and crystal structures of a three-dimensional (3D) coordination network $[Zn_4(2-mBIM)_5-(C_2H_6NCOO)(HCOO)({\mu}-OH)]{\cdot}DMF$ ($1{\cdot}$DMF; 2-mBIM = 2-methylbenzimidazolate) and a two-dimensional (2D) layer $[Zn_2(2-mBIM)_3(HCOO)(H_2O)]{\cdot}DMF$ ($2{\cdot}DMF$) are reported. Different structures were produced depending on the ratio of reactants. Structurally, 1 illustrates the formation of a unique framework based on a 2-mBIM bridge with the side group on an imidazole ring, while 2 possesses a honeycomb layer built up purely from imidazolates. For gas sorption, $CO_2$ is adsorbed on the activated phase of 1 but $N_2$ is not taken up.

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.

Luminescence Studies of Tb(Ⅲ) Complexes with Some Aminocarboxylate Ligands (Tb(Ⅲ)과 몇가지 아미노 카르복실 리간드 간의 착물에 대한 루미네센스 연구)

  • Kim, Dong Cheul;Bae, Jun Hyun;Kim, Youn Do;Kang, Jun Gil
    • Journal of the Korean Chemical Society
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    • v.41 no.11
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    • pp.581-585
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    • 1997
  • The luminescence spectra of Tb(Ⅲ) complexes have been investigated as a function of molar metal-to-ligand ratio and pH. The ligands used in this study are iminodiacetate (IDA) and methyliminodiacetate (MIDA). The 549 nm emission band, most sensitive to the coordination environment among the observed bands, is monitored to reveal the optimum condition for $TbL^{3-}_3$ complex formation in aqueous state.

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50개의 원자로 이루어진 직사각형 망상에 근거한 2차원 그물 망: Co-OBC-bipyen 배위 고분자, [Co(OBC)(bipyen)]ㆍ$H_2O$(OBC = 4,4′-oxybis(benzoate);bipyen = trans-1,2-bis (4-pyridyl) ethylene))

  • Lee, Hee-Keun;Mi S. Lim;Chung, Yong-Je;Lee, Soon W.
    • Korean Journal of Crystallography
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    • v.14 no.1
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    • pp.39-43
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    • 2003
  • The hydrothermal reaction of Co(NO₃)₂ㆍ6H₂O, trans-1,2-bis(4-pyridyl) ethylene (bipyen), and a bent 4,4'-oxybis(benzoic acid) (OBCH₂) gave a 2-D coordination polymer [Co(OBC)(bipyen)]ㆍH₂O(1). X-ray structure determination revealed that polymer 1 has a 2-D network based on 50-membered rectangular grids, each of which has the dimension of 13.74×13.20Å.

Synthesis and Crystal Structures of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) Metal Complexes with NNO Functionalized Ligands

  • Jang, Yoon-Jung;Lee, Uk;Koo, Bon-Kweon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.6
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    • pp.925-929
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    • 2005
  • Some new metal(II) complexes, $M^{II}L_2$ [M = Mn (1), Co (2), Ni (3), Cu (4), and Zn (5)] of 2-acetylpyridine benzoylhydrazone ligand (HL) containing trifunctional NNO-donor system have been synthesized and crystallographically characterized for the complex 1 and 5. The complexes consist of two ligands to give sixcoordinate, which are bonded to the metal atom on a meridional plane through acetylpyridine ring nitrogen, azomethine nitrogen, and benzoyl oxygen atoms, respectively. The coordination geometry for other complexes was identified on the basis of the physicochemical data by elemental analyses, FAB -MS, IR, $^1H$ NMR, and electronic spectral measurements. The resulting data indicated that the complexes are accordance with the above formulation.