• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.44-50
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• 1992

The ability to account for magnetic and spectra properties of complexes was investigated for the splitting of the degenerate d-orbitals and with nonaqueous solution by UV/vis-spectrophotometric method. The correlation of the magnetitude of 10Dq obtained from the spectra, the pairing energy, and the spin state of the complexes. The electrochemical behavior of complexes were investigated by the use of cyclic voltammetry in aprotic media. These reduction peak of $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$ and $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$ were irreversible one-electron processes at peak $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$ and $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$ of these complexes vs. Ag/AgCl, but nickel complexes were not to be reducible.

• Journal of the Korean Chemical Society
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• v.32 no.5
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• pp.428-435
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• 1988

Some nickel(Ⅱ) and palladium(Ⅱ) complexes of the ambidentate ligands derived from condensation of the isonitrosoacetylacetone and various diamines, $Ni(IAA)_2-en$, $Ni(IAA)_2-pn$, $Ni(IAA)_2-tn$, $Pd(IAA)_2-en$, PdCl(IAA)-pn, and $Pd(IAA)_2$-tn, where (IAA)$_2$-en, $(IAA)_2$-tn, and (IAA)-pn represent N,N'-enthylenbis(isonitrosoacetylacetone imine), N,N'-propylenebis(isonitrosoacetylacetone imine), N,N'-trimethylenebis(isonitrosoacetylacetone imine) and N-(2-aminopropyl)isonitrosoacetylacetone imine, respectively, have been prepared. The nickel(Ⅱ) and palladium(Ⅱ) complexes were characterized on the bases of the elemental analysis, IR, NMR, and electronic spectra. It is suggested that a isonitroso group of (IAA)$_2$-en or (IAA)$_2$-tn coordinates to the metal ion through the nitrogen atom to form five-membered ring, while the other isonitroso group of (IAA)$_2$-en or (IAA)$_2$-tn coordinates to the metal ion through the oxygen atom to form six membered ring in square-planar complexes of Ni(IAA)$_2$-tn and Pd(IAA)$_2$-en. And two isonitroso groups of (IAA)$_2$-en, (IAA)$_2$-pn, or (IAA)$_2$-tn coordinate to the metal ion through the nitrogen atom to form five-membered rings in square-planar complexes of Ni(IAA)$_2$-en, Ni(IAA)$_2$-pn, and Pd(IAA)$_2$-tn. On the other hand, square-planar PdCl(IAA)-pn is formed by the reaction of propylenediamine with a isonitrosoacetylacetone in the presence of palladium(Ⅱ)ion.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.947-955
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• 2011

The complexes [Pd(bpy)(Hex-dtc)]$NO_3$ and [Pt(bpy)(Hex-dtc)]$NO_3$ (bpy is 2,2'-bipyridine and Hex-dtc is hexyldithiocarbamato ligands) were synthesized and characterized by elemental analysis and spectroscopic studies. The cytotoxicity assay of the complexes has been performed on chronic myelogenous leukemia cell line, K562, at micromolar concentration. Both complexes showed cytotoxic activity far better than that of cisplatin under the same experimental conditions. The binding parameters of the complexes with calf thymus DNA (CT-DNA) was investigated using UV-visible and fluorescence techniques. They show the ability of cooperatively intercalating in CT-DNA. Gel filtration studies demonstrated that platinum complex could cleave the DNA. In the interaction studies between the Pd(II) and Pt(II) complexes with CT-DNA, several binding and thermodynamic parameters have been determined, which may provide deeper insights into the mechanism of action of these types of complexes with nucleic acids.

• Journal of the Korean Chemical Society
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• v.37 no.4
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• pp.423-430
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• 1993

New Palladium(0)-olefin complexes, $(PMe_3)_2Pd{CH_2=C(CH_3)COOH} \;and\;(PMe_3)_2Pd{(CH_3)CH=CHCOOH}$ have been prepared by treating $Pd(PMe_3)_2$(styrene) with methacrylic acid and trans-crotonic acid, respectively. These complexes were characterized by elemental analysis, IR and $^1H-,\;^{13}C-,\;and\;^{31}P$-NMR spectroscopy. The carboxylic acid entity was found non-bonded with palladium while ${\pi}$-bond is formed between the olefin double bond and Pd(0). The results are compared with the metallacycle formation the reaction of Pd(PMe3)2(styrene) with 3-butenoic acid.

• Analytical Science and Technology
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• v.9 no.3
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• pp.221-234
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• 1996

Basic studies for the effective extraction of dibenzylammonium dibenzyldithiocarbamate(DBADBDC) complexes of Ag(I), Pd(II), Au(III) and Pt(IV) into chloroform have been conducted. The effects of pH on the extraction of ligand itself and metal cemplexes showed that DBADBDC itself was uniformly extracted in the pH range of 2~9 and metal complexes were effectively extracted at the pH range as follows. That is, Ag(I) : in an acidic aqua medium, Pd(II) : > 4, Au(III) : wide range, and Pt(IV) : > 3. The distribution ratio and extractabilities were obtained from the partition and extraction equilibria of metal-DBDC complexes between aqueous solution and chloroform. Ag(I) : log D=4.226 : E(%)=99.9% in the aqueous solution of pH 0, Pd(II) : log D=1.804 : E(%)=98.5% at pH 4~7, Au(III) : log D=3.755 : E(%)=99.9% at pH 2~10, and Pt(IV) : log D=0.165 : E(%)=57.2% at pH 8.0. And also mole ratio of metal ion to ligand in complexes were determined by mole ratio method : 1 : 1 for Ag(I) and 1 : 2 for Pd(II), Au(III) and Pt(IV). $Cl^-$ was included as a coordination species in complexes of Au(III) and Pt(IV). Besides, extraction mechanisms of compleses sere examined in the presence of chloride ion in an aquous solution, and extraction reactions and estraction constants could be proposed and calculated, respectively.

• 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 $al.^5$.

• Bulletin of the Korean Chemical Society
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• v.9 no.4
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• pp.198-202
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• 1988

Several new palladium(II) complexes of aminophosphines, $(Pd(L)X_2)$, (L = $Ph_2PNH$ ++ $NR_2$; R = $CH_3(L_1)$, $C_2H_5(L_2)$ : X = Cl, Br, I, and NCS) that contain two different donor atoms of nitrogen and phosphorus as ${\pi}$-electron acceptor, were synthesized and characterized by conductivity measurement, ir, and UV/Vis-spectra. For the dithiocyanatopalladium(II) complexes with aminophosphines, it was confirmed that the thiocyanate group trans to phosphorus is coordinated as Pd-NCS mode and the one trans to nitrogen as Pd-SCN mode, and the aminophosphines form six-membered chelate ring. The spectra of dihalogenopalladium(II) complexes with aminophosphines show that the band maxima are shifted to the short wavelengths as the concentration is decreased.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.573-576
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• 2009

The reaction of $(en)Pd(NO_3)_2$ (en = ethylenediamine) with 1,4-bis(dimethyl-4-pyridylsilyl)benzene (L) affords cyclodimer, $[(en)Pd(L)]_2(NO_3)_4$, whereas the reaction of $(tmeda)Pd(NO_3)_2$ (tmeda = N,N,N’,N’-tetramethylethylenediamine) with L gives cyclotrimer, $[(tmeda)Pd(L)]_3(NO_3)_6$. Both complexes exist as catenane in water. The catenated cyclodimer is rigid whereas the catenated cyclotrimer is dynamic in water. The catenated cyclotrimers afford hydrogel containing 98.5% water below 2 ${^{\circ}C}$. The hydrogel changes to its sol around 38 ${^{\circ}C}$, and to its clear solution at 78 ${^{\circ}C}$. Such a notable difference between $[(en)Pd(L)]_2(NO_3)_4$ and $[(tmeda)Pd(L)]_3(NO_3)_6$ might be explained by their different dynamic behavior via ring size effects.

• Journal of the Korean Chemical Society
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• v.23 no.2
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• pp.59-64
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• 1979

The dipole moments for octahedral $[M(II)Cl_2N_2O_2]$, square planar and tetrahedral $[Pd(II)X_2Y_2]$ type complexes are calculated, using the approximate molecular orbital theory [M(II) = Ni(II) or Co(II), X = N and Y = O or S]. The calculated dipole moments for these complexes are in reasonable agreement with the experimental values. The possible structures for these complexes are investigated on the basis of the calculated dipole moments.

• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.593-599
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• 1990

A series of new, square planar, and mixed-ligand complexes of Ni(Ⅱ), Pd(Ⅱ), and Pt(Ⅱ) have been prepared. From the observation of electronic spectrum for the variation of the ligand substituents, the very intense absorption band in the visible range is by the electronic transition of dithiolene to diimine ligand, HOMO to LUMO. In the various solvent systems the IT band shows the similar behavior to IT transition of mixed-valence dinuclear complexes followed with Hush theory, happens rto dominently by the inner sphere charge transfer transition. The negative solvatochromism represents that the excited-state electric dipole is reduced or reversed by the electronic transition.