• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.906-913
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• 1992

The polymeric compound [{$W(NO)_2Cl_2$}$_n$] were prepared by reductive nitrosylation of $WNaNO_2$ and acidified $WFeSO_4$ with $WWCl_6$ at room temperature. The reactions of [{$W(NO)_2Cl_2$}$_n$] with unidentate and bidentate ligands afforded neutral monomeric [$W(NO)_2Cl_2L_2$(or L-L)] in a relative high yields (70$\sim$90%). 3,5-lutidine, ${\gamma}$-cyanopyridine, 1,2-phenylenediamine, 1,10-phenanthroline, sym-diphenylethylenediamine, 9,10-phenanthrenequinone, 1,3-bis(diphenylphosphino)propane, 1,1'-bis(diphenylphosphino)ferrocene and 8-hydroxyquinoline were used as coordinating ligands. These dinitrosyltungsten complexes were characterized by elemental analysis, $^1H$-NMR, infrared, and UV-visible spectroscopy are reported. The spectral data indicated that geometric structures of the products were cis-dinitrosyl-trans-dichloro-cis-$L_2$ of $C_{2v}$ symmetry.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1553-1558
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• 2009

A series of Eu(III) complexes with various neutral ligands (2,2’:6’,2"-terpyridine (T), diglyme (D), 1N-(2-dimethylamino) ethyl)-1N, 2N, 2N-trimethylethane-1,2-diamine (PT), di-(2-picolyl)-amine derivative (HT), and multidentate terpyridine derivative (DT)) were synthesized to investigate the effect of coordination environment on the sensitized luminescence of Eu(III) complexes. The nine coordination sites of the $Eu^{3+}$ ion are occupied by three bidentate carboxylate moieties and one neutral ligand. The highest emission intensity is obtained for $Eu^{3+}$- $[NA]_3$ (PT), due to the difference in energy transfer efficiency and symmetry of the first coordination sphere of $Eu^{3+}$ ion. But, the lowest emission intensity is obtained for $Eu^{3+}$-$[NA]_3$(T). Terpyridine may not play an important role antenna for photosensitizing $Eu^{3+}$ ion. It could be attributed to the weak spectral overlap integral J value between its phosphorescence band and $Eu^{3+}$ion absorption band. Therefore, different coordination environment of $Ln^{3+}$ ion play an important role in providing sensitization of lanthanide ion emission.

• Journal of the Korean Chemical Society
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• v.37 no.4
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• pp.442-447
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• 1993

The thermodynamic parameters (${\Delta}$G, ${\Delta}$H and ${\Delta}$S) of lanthanides(III)-benzoylformate complexes in aqueous solution have been determined in the ionic medium of 0.1M $NaClO_4$ at 25$^{\circ}C$, using pH and enthalpy titration method. The stability constants of the lanthanide(III)-benzoylformate complexes (1 : 1) agree well with the general relationships for the bidentate ligands (e.g., log${\beta}_1$ vs. p$K_a$). Thermodynamic evidences show that the oxygen atom in ketone group is coordinated along with the carboxylate group. It is ascribed to the increasing charge density on the oxygen atom in ketone group due to the conjugation effect in the benzoylformate ligand. Thermodynamic results also indicate that the complexes are stabilized by the enthalpy effect caused by the ionic interaction of metal-oxygen bond as well as the entropy effect.

• Bulletin of the Korean Chemical Society
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• v.15 no.11
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• pp.990-996
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• 1994

New ferrocene-based chelate amines, $Fe[C_5H_4CH(Me)NMe_2]_2\;(3), \;Fe[C_5H-3(CH(Me)NMe_2)(PPh_2)-1,2]_2\;(4),\;(C_5H_5)Fe(C_5H_3(CH_2NMe_2)(CH(CN)NMe_2-1,2)\;(6),\;and\;(C_5H_5)Fe(C_5H_3(CH_2NMe_2)(CH(Me)NMe_2-1,2)$ (7) have been prepared. The reaction and the coordination chemistry of 4 and other related compounds (S,R)-(1-N,N-dimethylaminoethyl)-2-dicyclohexylphosphino)ferrocene (CPFA) and 1,1'-bis-(diphenylphosphino)ferrocene (BPPF) with $Rh_2(OAc)_4(MeOH)_2$ were investigated. The reaction of the chiral ligand (S,R)-CPFA forms a complex of the type (${\eta}^1$-(S,R)-CPFA-P)$_2Rh_2(OAc)_4$ (8) in which the ligand is coordinated to both rhodium centers in a monodentate fashion through phosphorus. In contrast, the bisphosphine analogues such as BPPF and 4 afford chelate complexes of the type (${\eta}^2-PP)Rh_2(OAc)_4$ (9 & 10) where both ligands act as a chelate bidentate to a single rhodium atom. All these complexes were characterized by microanalytical and spectroscopic techniques. In one case, the structure of 8 was determined by X-ray crystallography. Crystals are monoclinic, space group C2 (No. 5), with a=26.389 (3), b=12.942 (1), c=11.825 (1) A, ${\beta}$=111.22(1)$^{\circ}$, V=3964.7 (8) $A^3$, Z=4, and $D_{calc}$=1.58 g $cm^{-3}$. Two Rh(II) centers are bridged by four $AcO^-$ groups in the ${\eta}^1$ : ${\eta}^1$ mode across a Rh-Rh single bond, and octahedral coordination at Rh(1) and Rh(1') is completed by axially coordinating (S,R)-CPFA and a briding $AcO^-$, respectively.

• Journal of the Korean Chemical Society
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• v.65 no.2
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• pp.93-105
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• 2021

Mononuclear Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Fe(III), Ru(III), and UO2(II) complexes of 2-hydroxy-4-(p-tolyldiazenyl)benzylidene)-2-(p-tolylamino)acetohydrazide (H2L) were prepared by direct method. The ligand and its complexes were isolated in solid state and characterized by analytical techniques such as elemental and thermal analyses, molar conductance, magnetic susceptibility measurements and spectroscopic techniques such as UV-Visible, IR, 1H-NMR and 13C-NMR. The spectral data indicated that the ligand acted as neutral/monobasic bidentate or monobasic/dibasic tridentate ligand bonded to the metal ions through the oxygen atom of ketonic or enolic carbonyl group, azomethine nitrogen atom and deprotonated/protonated phenolic oxygen atom forming either tetragonally distorted octahedral or octahedral. Antimicrobial activities of the ligand and its complexes were evaluated against Escherichia coli, Bacillus subtilis and Aspergillus niger by well diffusion method. The results of antifungal activity showed that the Fe(III) complex (10) exhibited higher antifungal against Aspergillus niger than the other complexes. However, the results of antibacterial activity revealed that Cu(II) complex (4) is the most active against Escherichia coli while the Cu(II) complex (5) and Fe(III) complex (10) exhibited higher antibacterial effect on Bacillus subtilis than the other complexes.

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.266-271
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• 1993

The reaction of $(CO_5$)M=C(OMe)Tol (M=Cr, Mo, W and $Tol=p-C_6H_4Me)$ and $BBr_3$ followed by treatment with tetramethylethylenediamine (TMEDA) yields a mixture of two diastereomers, trans, $cis-Br(CO)_2(tmeda)M{\equiv}$CTol [M=Cr(1a), Mo(2a), W(3a)] and cis, $trans-Br(CO)_2(tmeda)M{\equiv}$CTol [M=Cr(1b), Mo(2b), W(3b)], respectively. These compounds have been isolated as crystalline solids and characterized by spectroscopic (infrared, mass, $^1H$ and $^{13}C-NMR)$ data. The trans, cis-Br(CO)2(tmeda)Cr${\equiv}$CTol (1a), has been examine via a single crystal X-ray diffraction study : $BrCrO_2N_2C_{16}H_{23}$, Mr=407.27, triclinic, $P{\bar{1}},\;a=12.792(2),\;b=13.400(5),\;c= 11.645(4)\;{\AA},\;{\alpha}=101.26(2)^{\circ},\;{\beta}=103.04(2)^{\circ},\;{\gamma}=91.88(2)^{\circ},\;{\nu}=1907(1){\AA}^3,\;Z=2,\;{\rho}(calcd)=1.418\;gcm^{-3},\;{\lambda}(MoK{\alpha})=0.71069\;{\AA},\;{\mu}=26.25 cm^{-1},\;F(000)=831.97,\;T=295K,\;R=0.0977$ for 1332 significant reflections $[F_0>5{\sigma}(F_0)]$. There are two essentially equivalent molecules in the crystallographic asymmetric unit. Each molecule is octahedral with the bromide ligand trans to the alkylidyne carbon, the two cis-carbonyl ligands, and the bidentate TMEDA ligand.

• Journal of the Korean Chemical Society
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• v.53 no.1
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• pp.17-26
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• 2009

Hydrazones of isonicotinic acid hydrazide, viz., N-isonicotinamido-furfuralaldimine (INH-FFL), N-isonicotnamido-cinnamalidine (INH-CIN) and N-isonicotnamido-3',4',5'-trimethoxybenzaldimine (INH-TMB) were prepared by reacting isonicotinic acid hydrazide with respective aromatic aldehydes, i.e., furfural, cinnamaldehyde or 3,4,5-trimethoxy-benzaldehyde. A new series of fifteen complexes of cobalt(II) with these new hydrazones, INH-FFL, INH-CIN and INH-TMB, were synthesized by their reaction with cobalt(II) salts. The infrared spectral data reveal that hydrazone ligands behave as a bidentate ligand with N, O donor sequence towards the $Co^{2+}$ ion. The complexes were characterized on the basis of elemental analysis, magnetic susceptibility, conductivity, infrared and electronic spectral measurements. Analytical data reveal that the complexes have general composition [Co($L)_2X_2]\;and\;[Co(L)_3](ClO_4)_2$ where L= INH-FFL, INH-CIN or INH-TMB and X = $Cl^-,{NO_3}-,\;NCS^-\;or\;CH_3COO^-.$ The thermal behaviour of the complexes were studied using thermogravimetrictechnique. Electronic spectral results and magnetic susceptibility measurements are consistent with the adoption of a six-coordinate geometry for the cobalt(II) chelates. The antimicrobial properties of cobalt(II) complexes and few standard drugs have revealed that the complexes have very moderate antibacterial activities.

• Analytical Science and Technology
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• v.6 no.5
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• pp.417-424
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• 1993

Eight-coordinate tetrakis molybdenum(IV) complexes containing 5,7-dichloro-8-hydroxyquinolinol(Hdcq) and 2-mercaptopyrimidine(Hmpd) has been prepared. $Mo(mpd)_4$, $Mo(dcq)(mpd)_3$, $Mo(dcq)_2(mpd)_2$, $Mo(dcq)_3(mpd)$ and $Mo(dcq)_4$ complexes have been isolated by thin-layer chromatography on silicagel plates. These complexes have been charaterized by $^1H-nmr$ spectrum and UV-Vis. spectrum. The chemical shift values of the protons ${\alpha}$ to the nitrogen in the ligands are shifted to down field. The relative intensities of the peaks which are positioned at the same proton of $Mo(dcq)(mpd)_3$ and $Mo(dcq)_3(mpd)$ are observed in 2:1 ratio, in case of $Mo(dcq)_2(mpd)_2$ appears in approximately a 1:1 ratio. The stereochemistry of the complexes in discussed in terms of their nmr spectrum and Orgel's rule. By vertue of the intensities (${\varepsilon}$>10,000~25,000) the low energy($16,600{\sim}19,800cm^{-1}$) bands are observed for the electronic spectra of the complexes are assigned as charge transfer bands.

• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.48-54
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• 2012

The $[Fe_4S_4]^{2+}$ clusters with 2-, 3-, and 4-pyridinemethanethiolate (S2-Pic, S3-Pic, and S4-Pic, respectively) terminal ligands have been synthesized from the ligand substitution reaction of the $(^nBu_4N)_2[Fe_4S_4Cl_4]$ (I) cluster. The new $(^nBu_4N)_2[Fe_4S_4(SR)_4]$ (R = 2-Pic; II, 3-Pic; III, 4-Pic; IV) clusters were characterized by FTIR and UV-Vis spectroscopy. Cluster II was crystallized in the monoclinic space group C2/c with a = 24.530 (5) $\AA$, b = 24.636(4) $\AA$, c = 21.762(4) $\AA$, ${\beta}=103.253(3)^{\circ}$, and Z = 8. The X-ray structure of II showed two unique 2:2 site-differentiated $[Fe_4S_4]^{2+}$ clusters due to the bidentate-mode coordination by 2-pyridinemethanethiolate ligands. Cluster III was crystallized in the same monoclinic space group C2/c with a = 26.0740(18) $\AA$, b = 23.3195(16) $\AA$, c = 22.3720(15) $\AA$, ${\beta}=100.467(2)^{\circ}$, and Z = 8. The 3-pyridinemethanethiolate ligand of III was coordinated to the $[Fe_4S_4]^{2+}$ core as a terminal mode. Cluster IV with 4-pyridinemethanethiolate ligands was found to have a similar structure to the cluster III. Fully reversible $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ redox waves were observed from all three clusters by cyclic voltammetry measurement. The electrochemical potentials for the $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ transition decreased in the order of II, III and IV, and the reduction potential changes by the ligands were explained based on the structural differences among the complexes. The complex III was reacted with sulfonium salt of $[PhMeSCH_2-p-C_6H_4CN](BF_4)$ in MeCN to test possible radical-involving reaction as a functional model of the [$Fe_4S_4$]-SAM (S-adenosylmethionine) cofactor. However, the isolated reaction products of 3-pyridinemethanethiolate-p-cyanobenzylsulfide and thioanisole suggested that the reaction followed an ionic mechanism and the products formed from the terminal ligand attack to the sulfonium.

• Journal of the Korean Chemical Society
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• v.27 no.2
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• pp.83-94
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• 1983

The effects of cis and trans configurations of ligands for $[M(II)O_3N_3]$ and $[Ni(II) O_2N_4]$ type complexes [M(II) = Co(III), Ni(II) and Cu(II)] on the calculated dipole moments have been investigated, adpoting the eigenvectors of EHT calculation. The calculated dipole moments for cis complexes are higher than those of trans complexes. The calculated dipole moments for the octahedral trans $[Co(III)O_3N_3]$ type complex fall in the range of experimental values. However the calculated dipole moments for cis $[Ni(II) O_2N_4]$ type complexes fall in the range of the experimental values. These results predicts the trans structure for $[Co(III)O_3N_3]$ and $[Ni(II) O_2N_4]$ type complexes. Those structures are in agreement with the experimental one (Three bidentate (O-N) ligands in $[M(II)O_3N_3]$ type complexes coordinate to the metal ion and two tridentate (O-N-N) ligands in [Ni(II)O2N4] type complexes coordinate to Ni(II) ion).