• 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.

• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.1012-1019
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• 2004

The synthesis of novel group 9 metal complexes containing the S,S'-chelate ligands, $Li_2S_2C_2B_{10}H_{10}$ (2a) and $LiS(S=PMe_2)C_2B_{10}H_{10$} (2b), is described. Two new dinuclear complexes of the type $[{(cod)M}_2(S,S'-S_2C_2B_{10}H_{10})]$ (cod = 1,5-cyclooctadiene; M = Rh (3a), or Ir (3b)) were synthesized by the reaction of chloridebridged dimers $[M({\mu}-Cl)(cod)]_2$ with one molar equivalent of the corresponding dilithium dithiolato ligand $Li_2S_2C_2B_{10}H_{10}$ (2a). X-ray crystal structure analysis of 3a revealed a dinuclear structure in which each (cod)Rh unit is attached to a distinct sulfur atom of a 1,2-dithio-o-carboranyl ligand (2a). Additionally, the electrochemical properties of 3a and 3b were investigated by cyclic voltammetry. In an analogous manner, reaction of the lithium dithiolato ligand $LiS(S=PMe_2)C_2B_{10}H_{10}$ (2b) with $Cp^{\ast}CoI_2(CO)$ produced a mononuclear dithiolato complex, $[Cp^{\ast}CoI{(S,S'-S(S=PMe_2)C_2B_{10}H_{10})}]$ (4), which was characterized by single-crystal X-ray analysis.

• Journal of Environmental Science International
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• v.8 no.3
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• pp.411-417
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• 1999

The interfacial chemical behavior, lattice exchange and dissolution, of $FeS_{(S)}$ as one of the important sulfide minerals was studied. Emphases were made on the surface characterization of hydrous $FeS_{(S)}$, the lattice exchange of Cu(II) and $FeS_{(S)}$, and its effect on the dissolution of $FeS_{(S)}$, and also affect some organic ligands on that of both Cu(II) and $FeS_{(S)}$. Cu(II) which has lower sulfide solubility in water than $FeS_{(S)}$ undergoes the lattice exchange reaction when Cu(II) ion contacts $FeS_{(S)}$ in the aqueous phase. For heavy metals which have higher sulfide solubilities in water than $FeS_{(S)}$, these metal ions were adsorbed on the surface of $FeS_{(S)}$. Such a reaction was interpreted by the solid solution formation theory. Phthalic acid(a weak chelate agent) and EDTA(a strong chelate agent) were used to demonstrate the effect of organic lignads on the lattice exchange reaction between Cu(II) and $FeS_{(S)}$. The $pH_{zpc}$ of $FeS_{(S)}$ is 7 and the effect of ionic strength is not showed. It can be expected that phthalic acid has little effect on the lattice exchange reaction between Cu(II) and $FeS_{(S)}$. whereas EDTA has very decreased the removal of Cu(II) and $FeS_{(S)}$. This study shows that stability of sulfide sediments was predicted by its solubility. The pH control of the alkaline-neutralization process to treat heavy metal in wastewater treatment process did not needed. Thereby, it was regarded as an optimal process which could apply to examine a long term stability of marshland closely in the treatment of heavy metal in wastewater released from a disussed mine.

• Journal of the Korean Chemical Society
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• v.26 no.1
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• pp.31-35
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• 1982

Novel palladium(II) complexes of the type Pd(IBA-NH)(IBA-NH') and Pd(IBA-NR)2, where IBA-NH and IBA-NR (R: methyl, ethyl, n-propyl, n-butyl, benzyl) represent isonitrosobenzoylacetone imine and its N-alkyl derivatives respectively, have been prepared. The ir, nmr, and electronic spectra of the palladium(Ⅱ) complexes have been studied. It has been determined that the isonitroso group of IBA-NH coordinates to palladium through the oxygen to form 6-membered chelate ring and that of IBA-NH' coordinates to palladium through the nitrogen to form 5-membered ring in square-planar Pd(IBA-NH)(IBA-NH') and it also has been determined that the isonitroso groups of two IBA-NR coordinates to palladium through the nitrogen to form 5-membered rings in square-planar Pd$(IBA-NR)_2$. The coordination manner of the ligands is similar to that of isonitrosoacetylacetone imines obtained by Bose, et $al.^5$.

• Journal of the Korean Chemical Society
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• v.26 no.5
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• pp.310-319
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• 1982

Cobalt(III) complexes with sexidentate ligands, N,N,N',N'-tetrakis(2-amino-ethyl)-1,2-ethanediamine (ten), -1,3-propanediamine (ttn), -1,4-butanediamine (ttmd), -(R,R)-and -(R,S)-2,4-pentanediamine (tptn) were prepared, and the characterization of d-d absorption band on the variation of chelate ring size and conformation of these complexes were studied by means of electronic spectra. The first d-d absorption bands of $[Co(L)]^{3+}$ complexes are shifted to smaller wave numbers in the order. ttn > (R,R)-tptn > ten > ttmd${\simeq}$(R,S)-tptn for (L). The UV, $^{13}C$ NMR, and Circular Dichroism studies indicate that the R,S-tptn ligand of $[Co(R,S-tptn)]^{3+}$ complex coodinates to cobalt(Ⅲ) ion as a sexidentate with one methyl group in axial position.

• Applied Chemistry for Engineering
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• v.21 no.1
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• pp.1-5
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• 2010

Cu(II)-organic complexes were synthesized with Lewis base organic ligands including diamine, aminothiol, and dithiol to determine the reactivity for DFP hydrolysis. Results show that the aminothiol catalyst enhances the hydrolysis of DFP in three folds compared to diamine type because aminothiol has higher basicity than diamine. Due to low solubility of Cu(II)(1,2-ethane dithiol)$(NO_3)_2$, it is impossible to compare directly the rates in homogeneous condition. However, the rate of dithol complex is even 1.6 times faster than that of the diamine type. The reactivity of zeolite for DFP hydrolysis is also evaluated. NaY type does not promote the hydrolysis, but RuNaY shows relatively lower reactivity than those of Cu(II)-organic ligands complexes.

• Journal of the Korean Chemical Society
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• v.22 no.1
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• pp.19-24
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• 1978

Novel nickel(II) complexes of the type Ni(IBA-NH)(IBA-NR), where IBA-NH and IBA-NR (R=H, methyl, ethyl, n-propyl, iso-propyl, n-butyl or benzyl) represent isonitrosobenzoylacetone imine and its N-alkyl derivative respectively, have been prepared. The ir, nmr, and electronic spectra and magnetic moment of the nickel(II) complexes have been studied. It has been determined that the isonitroso group of IBA-NH coordinates to nickel through the oxygen to form 6-membered chelate ring and that of IBA-NR coordinates to nickel through the nitrogen to form 5-membered ring in square-planar Ni(IBA-NH) (IBA-NR). The coordination manner of the ligands is similar to that of isonitrosoacetylacetone imines obtained by Bose, et al.

• Journal of the Korean Chemical Society
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• v.37 no.7
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• pp.655-661
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• 1993

The neutral monomeric compounds $[Mo(NO)_2Cl_2(phen)]$ and $[W(NO)_2Cl_2(phen)]$ (phen= 1,10-phenanthroline) have been prepared by reactions of polymeric compounds $[{Mo(NO)_2Cl_2}n],\;[{W(NO)_2Cl_2}n]$ with chelate ligands. Additions of one equivalent of silver(I) perchlorate to these cis-dinitrosyl compounds in acetone solution produce $[Mo(NO)_2(phen)(S)Cl][ClO_4]\;and\;[W(NO)_2(phen)(S)Cl][ClO_4]$ (S = acetone). The homo- and hetero-dinuclear complexes, $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][ClO_4]_2$ (M = Mo, W) and $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][C1O_4]_2$ (M = Mo, M' = W) have been prepared by these monocationic complexes with pyrazine ligand respectively. These complexes characterized by elemental analysis, $1^H-\;and\;^{13}C-NMR$, infrared, and UV-visible spectroscopy are reported. The spectral data indicate that homo- and hetero-dinuclear complexes were symmetrical structures of $C_{2v}$.

• 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.

• Analytical Science and Technology
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• v.5 no.1
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• pp.41-49
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• 1992

An attempt was made to prepare two series of tetrakis eight-coordinate tungsten(IV) and cerium(IV) complexes containing the 5,7-dichloro-8-quinolinol(N:${\pi}$-acceptor atom, O:${\pi}$-donor atom) ligand. Tetrakis eight-coordinate tungsten(IV) complex of 2-mercaptopyrimidine(N:${\pi}$-acceptor atom, S:${\pi}$-donor atom) ligand have also been prepared. And the new series of mixed-ligand eight-coordinate tungsten(IV) complexes containing bidentate ligands 5,7-dichloro-8-quinolinol and 2-mercaptopyrimidine have been prepared, isolated by TLC and characterized. $W(dcq)_4$, $W(dcq)_3(mpd)_1$, $W(dcq)_2(mpd)_2$, $W(dcq)_1W(dcq)_3$ and $W(mpd)_4$ complexes of MLCT absorption band appeared to 710nm, 680nm, 625nm, 581nm, and 571nm(${\varepsilon}\;max={\sim}>{\times}10^4$) on low-energy respectively. The specific absorption wave length of $Ce(dcq)_4$ is appeared 520nm(${\varepsilon}\;max={\sim}>{\times}10^4$). The Chemical shift values by proton of coordinated position appeared to $W(dcq)_4$ [$H_2:8.9ppm$]; $W(dcq)_3(mpd)_1$ [$H_2:9.3$,$H_6:9.2ppm$]; $W(dcq)_2(mpd)_2$ [$H_2:9.7$,$H_6:8.95ppm$]; $W(dcq)_1(mpd)_3$ [$H_2:9.8$,$H_6:9.4ppm$]; $W(mpd)_4$ [$H_6:8.8ppm$]; $Ce(dcq)_4$ [$H_2:9.3ppm$] with $^1H$-NMR. The inertness of mixed-ligand eight coordinate tungsten(IV) complexes have been investigated by UV-Vis. spectroscopic method in dimethylsulfoxide at $90^{\circ}C$. The inertness of $W(dcq)_n(mpd)_{4-n}$ complexes showed the following order, $W(dcq)_3(mpd)_1;k_{obs.}=3.8{\times}10^{-6}$ > $W(mpd)_4;k_{obs.}=6.0{\times}10^{-6}$ > $W(dcq)_4;k_{obs.}=6.4{\times}10^{-6}$ > $W(dcq)_2(mpd)_2;k_{obs.}=7.0{\times}10^{-6}$ > $W(dcq)_1(mpd)_3;k_{obs.}=1.7{\times}10^{-5}$, which showed the inertness until 16days, 10days, 9days, 8days, and 4days. The $W(mpd)_4$ is very inert as $k_{obs.}=3.6{\times}10^{-6}$(16days) in xylene at $90^{\circ}C$ and $k_{obs.}=6.0{\times}10^{-6}$(10days) in DMSO at $90^{\circ}C$.