• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2279-2286
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• 2012

The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-aminopropylamino)ethane produce the 12-membered $N_3O$ and 17-membered $N_4O$ macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear $N_3O$ and $N_4O$ copper(II) complexes show one irreversible oneelectron reduction wave at $E_{pc}=-1.35$ and -1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at $E_{pc}=-1.25$ and -1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at $E_{pa}=+0.84$ and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.37-41
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• 2004

A new tridentate ligand incorporating a monoxime and thiosemi-carbozone moieties has been synthesized. Its copper(II), nickel(II) and palladium(II) complexes have been prepared and characteirzed by physical and spectral methods. Elemental analyses and spectroscopic data of the metal complexes are consistent with the formation of a mononuclear copper(II) complex and binuclear complex with both nickel(II) and palladium(II). In the copper(II) complex the fourth coordination site is occupied by nitrate ion. In the binculear complexes the fourth coordination site is occupied by the deprotonated oxime oxygen of the ligand coordinated to the other metal.

• Bulletin of the Korean Chemical Society
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• v.16 no.6
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• pp.518-523
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• 1995

New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.

• Bulletin of the Korean Chemical Society
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• v.15 no.5
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• pp.374-378
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• 1994

Square planar nickel(II) complexes with various 1-alkyl derivatives of the 14-membered pentaaza macrocycle 8-methyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane can be readily prepared by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary alkylamines. In coordinating solvents the nickel (II) complexes form octahedral species containing two axially coordinated solvent molecules and thus show square planar-octahedral equilibrium. The properties of the pentaaza macrocyclic complexes are considerably different from those of the complexes of analogous hexaaza and tetraaza macrocyclic complexes. Synthesis, characterization, and spectroscopic and chemical properties of the new complexes are described.

• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.217-221
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• 1995

Axial coordination of anions or water to the square-planar nickel(Ⅱ) complexes of the hexaaza macrocyclic ligands 1, 2, and 3, which contain two extra uncoordinated tertiary nitrogens, have been investigated in aqueous solutions containing HX (X=Cl-, Br-, NO3-, or ClO4-) and/or NaX. The nickel(Ⅱ) complexes exist in the acidic solutions as equilibrium mixtures of the square-planar [Ni(L)]2+ (L=1, 2, and 3) and octahedral species [Ni(H2L)X2]2+ (H2L=diprotonated form of L). Some octahedral complexes have been isolated and characterized. The solution behaviors of the complexes indicate that the formation of the octahedral complexes are significantly promoted by the protonation of the uncoordinated tertiary amines. The proportion of the octahedral complexes depends on the type of acid, and increases in the order of HBr < HNO3 < HCl.

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1106-1110
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• 2000

New 14-membered tetraaza macrocycles 1,8-diallyl-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^2)$ and 1,8-bis(n-propyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^3)$ have been prepared by direct react ion of 2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecane $(L^1)with$ allyl bromide or n-propyl bromide. The nickel(II) and copper(II) complexes of $L^2andL^3have$ been prepared. The macrocycles show high copper(II) selectivity against nickel(II) ion in methanol solutions containing water. The wavelengths (ca. 505 nm) of the d-d bands for the nickel(II) complexes are extraordinarily longer than those for the complexes of $L^1and$ other related di-N-alkylated 14-membered tetraaza macrocycles. Crystal structure of $[NiL^2](ClO4)_2$ shows that the average Ni-N bond distance $(1.992\AA)$ of the complex is distinctly longer than those of other related nickel(II) complexes. Effects of the N- and C-substituents on the properties of the macrocyclic compounds are discussed.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1439-1440
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• 2009

• Bulletin of the Korean Chemical Society
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• v.12 no.4
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• pp.368-370
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• 1991

The electrochemical behavior and the complex formation between N$i^{2+}$ and 1,7-diazs-15-crown-5 and 1,10-diaza-18-crown-6 in acetonitrile solution have been studied by DC polarography, differential puke polarography and cyclic voltammetry. Nickel(Ⅱ) complexes gave a single well-defined wave. The formation constants of their complexes were 1$0^{4.89} and 10^{3.86}$, respectively. Nickel(Ⅱ) ion was found to form complexes of 1-to-1 composition with 1,7-diaza-15-crown-5 and 1,10-diaza-18-crown-6. In addition, reduction steps were irreversible and the reduction current were diffusion controlled. The electrochemical reduction mechanism of Ni(Ⅱ)-macrocyclic diaza-crown complexes in acetonitrile solution is estimated.

• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.1022-1028
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• 1997

The reaction between Ni(Ⅱ) and sodium salt of 5,6-dihydro-1,4-dithiin-2,3-dithiolate (DDDT2-) in the presence of oxygen results in the formation of Ni(Ⅲ) species, Ni(DDDT)2-, which is isolated as tetraalkylammonium salt. The same reaction performed in the absence of oxygen yields dianionic Ni(Ⅱ) species, Ni(DDDT)22-, which is also isolated as the tetraethylammonium salt. The bis(5,6-dihydro-1,4-dithiin-2,3-dithiolato) nickelate (Ⅱ) dianion, Ni(DDDT)22-, reacts with methyl iodide to yield unusually stable bis(methylthio)dithiolene complex, Ni(CH3)2C8H8S8. All the isolated dithiolato-nickel(Ⅱ) and nickel(Ⅲ) complexes are characterized by 1H NMR, UV/Vis, IR and mass spectroscopic methods. The internal redox reaction of the nickel(Ⅱ)-dithiolate has been studied by spectro-electrochemical method and the results were compared with those of other metal-dithiolenes. The alkylated nickel(dithiolene) complex presumably undergoes cis-trans isomerization reaction in solution, judging from the experimental results of variable-temperature 1H NMR measurements.

• Bulletin of the Korean Chemical Society
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• v.27 no.7
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• pp.1031-1037
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• 2006

New nickel complexes containing novel tetradentate ligands, 4,5-substituted-1,2-bis(pyridine-2-carboxamide)-benzene ligands but lacking alkyl or halide ligands in the coordination sphere have been prepared. They were activated with MMAO (modified methylaluminoxane) to be proven as efficient catalysts for the polymerization of norbornene. Both electron-donating and -withdrawing substituents on the benzene ring and polar solvents enhance the catalytic activity for olefin polymerization. Improvement in thermal stability of the complexes was observed. Some of these complexes were crystallographically determined to have square planar geometry. A plausible mechanism involving dissociation of ligands is proposed.