• Archives of Pharmacal Research
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• v.15 no.4
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• pp.336-342
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• 1992

Ten [$Pd^{II}$(dicarboxylato)(1, 2-diaminocyclohexane)] complexes were prepared after the antitumor-active Pt(II)1, 2-diaminocyclohexane complexes as the cisplatin analogues of palladium series. They were characterized by means of elemental analysis, IR and NMR spectroscopy. As a result, the dicarboxylate ligands were conformed to be chelated with Pd(II) within the scope studied. The stability differences beween the dicarboxylato complexes according to the chelate ring size could not be differentiated due to generally lower thermodynamic stability of the dicarboxylato Pd(II) complexes.

• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.85-89
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• 2004

Geometrical structures of [Pd(L)$Cl_2$] with oxathia macrocycles have been calculated using ab initio secondorder Moller-Plesset (MP2) and Density Functional Theory (DFT) methods with triple zeta plus polarization (TZP) basis set level. In optimized Pd(L)$Cl_2$ complexes, Pd(II) locates at the center surrounded by a square planar array of two sulfurs on an oxathia macrocycle and two chlorides. The endo-Pd(II) complexes with an axial (Pd${\cdots}$O) interaction are more stable than the exo-Pd(II) complexes without the interaction. In the endo-Pd(II) complexes, the atomic charge of the oxygen atom moves to Pd(II) via the axial ($Pd{\cdots}$O) interaction and then, the charge transfer from Pd(II) to the S-atoms occurs stepwise via ${\pi}$-acceptors of the empty d-orbitals.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.320-326
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• 1986

The antitumor properities of metal are not limited to Pt(II) complexes. Recently, it was reported that some Pt(II) and Pd(II) complexes with sulfur and nitrogen ligands had potential antitumor reactivity. Pt(II) complexes is toxic drug for anticancer. Therefore, the complexes of Pd(II) with adenine, uracil, cytosine and malonate ligands are interesting for anticancer drug. We synthesized new palladium complexes containing nucleosides. The reactions of Pd(II) with adenine, uracil, cytosine and malonate ligands have been studied in aqueous solutions. The complexes isolated from these reactions have the following formulas; $[Pd(en)(C_5H_5N_5)_2](NO_3)_2,\;[Pd(en)(C_4H_3N_2O_2)Cl],\;[Pd(en)(C_3H_2O_4)]\;and\;[Pd(en)(C_4H_5N_3O)_2](NO_3)_2{\cdot}(C_4H_5N_3O)$. The compounds have been identified by elemental analysis, mass spectra, infrared spectra and electronic spectra.

• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.211-214
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• 1995

The catalytic activities of palladium(0,Ⅰ,Ⅱ)-diphosphine complexes were investigated in styrene oxidation using H2O2 as terminal oxidant. The rates showed a dependence on the chelate ring patterns of complexes (PdCl2L); 5-membered ring (L=dppe: 1,2-bis(diphenylphosphino)ethane) < 6-membered ring (L=dppp: 1,3-bis(diphenylphosphino)propane) < 4-membered ring (L= dppm: bis(diphenylphosphino)methane). This sequence correlates with the ligand field strength and interactions between metal and phosphine ligands. Pd(Ⅱ,Ⅰ)-diphosphine complexes which are capable of making 4-membered chelate ring showed an enhancement of catalytic activities for styrene oxidation. The catalytic activities of Pd(0,Ⅰ,Ⅱ)-diphosphine complexes are described in terms of electronic and steric factors.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.636-646
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• 2009

A series of the noble palladium complexes containing $\beta$-ketoiminate ligands with internal bases, [Pd(${\eta}^3$-allyl)($\beta$- ketoiminate)], [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] and [Pd(Me)($\beta$-ketoiminate)], have been successfully prepared. Crystallographically determined structures showed that these complexes are distorted square planar and pendant bases of the $\beta$-ketoiminate ligands fail to coordinate to the metal in the first two classes of complexes while bases do coordinate in the 3rd class complexes. These complexes are active towards norbornene polymerization on activation with $H(OEt_2)_2BAr^'_4$ (Ar' = 3,5-bistrifluoromethylphenyl) and modified methylalumioxane (MMAO). MMAO is more efficient for the activation for polymerization. Generally, the polymerization activity increases with the following order; [Pd(allyl)($\beta$-ketoiminate)] < [Pd(Me)($PPh_3$)($\beta$-ketoiminate)] < [Pd(Me)($\beta$-ketoiminate)].

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.627-640
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• 2008

The geometrical structures, atomic charges, and relative energies of tetracoordinated Pd complexes [PdCl3Z (Z = Cl-, Br-, OH?-, H2O, NH3, PH3), PdCl2Z2 (Z = Br-, OH?-, H2O, NH3, PH3), PdZ?2X (Z = Cl-, OH?-, H2O, NH3, PH3; X = oxalate, O2-?CCO2-), and PdZ2Y (Z = Cl?-, OH?-, H2O, NH3, PH3; Y = succinate, CO2-?CHCHCO2-?)] and the ligand exchange reactions of the Pd complexes were investigated using the ab initio second order Mller-Plesset perturbation (MP2) and Density Functional Theory (DFT) methods. The geometrical characteristics of the tetracoordinated Pd(II) complexes with mono- and bidentate ligands, the effects of the atomic charges for the charged and uncharged ligands, the (dz2-p ) interactions between the dz2-orbital of Pd(II) and the p -orbital of bidentates, and the relative stabilities between the isomers of PdCl2Z2 and PdZ2Y were investigated in detail. The potential energy surfaces for the ligand exchange reactions used for the conversions of {[PdCl2(NH3)2] + H2O} to {[PdCl(NH3)2(H2O)]+ + Cl?-?} and {[PdCl2(PH3)2] + H2O} to {[PdCl(PH3)2(H2O)]+ + Cl?-?]} were investigated. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes were also examined quantitatively.

• Journal of the Korean Chemical Society
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• v.37 no.7
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• pp.662-671
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• 1993

New Ni(II) and Pd(II) complexes of isonitrosomethylacetoacetate imine derivatives, Ni(IMAA-NH)(IMAA-NH'), Ni(IMAA-NH)(IMAA-NR), $Pd(IMAA-NH)_2\;and Pd(IMAA-NR)_2(R=CH_3,\;C_2H_5,\;n-C_3H_7,\;n-C_4H_9,\;or\;CH_2C_6H_5)$, where H-IMAA-NH and H-IMAA-NR represent isonitrosomethylacetoacetate imine and N-alkylisonitrosomethylacetoacetate imine derivative, respectively, have been prepared and the structures of the complexes have been studied by elemental analyses, electronic, infrared, and $^1H-\;and\;^{13}C-NMR$ spectroscopies.

• Journal of the Korean Chemical Society
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• v.42 no.4
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• pp.369-377
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• 1998

The palladium(II) and platinum(II) complexes(where, $([M(L)_2X_2]$, M=Pd(II), Pt(II); L=isoxazole(isox), 3,5-dimethylisoxazole(3,5-diMeisox), 3-methyl, 5-phenylisoxazole(3-Me, 5-Ph-isox), and 4-amino-3,5-dimethylisoxazole (4-ADI); X=Cl, Br) with isoxazole and its derivatives were investigated on antitumor activity by MM2 and EHMO calculation. Because for all the complexes the ${\sigma}MO$ energy level $(E_{{\sigma}(M-X)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of halogen atom is less than ${\sigma}MO$ energy level $(E_{{\sigma}(M-N)})$ between $d_x^{2-}_y^2$ orbital of central metal and px orbital of N atom, without exception. And judging, from the lower $(E_{\'{o}(m-x)})$ value in trans, the bonding strength was found to be weaker in trans isomer than in cis. For the Pd(II) and Pt(II) complexes which have planar ligands, it was shown that for all the complexes dissociation of X-atom in the Pd(II) complexes is easier than that of X-atom in the Pt(II) complexes in both cis- and trans-complexes. Therefore it suggests that the easier dissociation of $X^-$ ion has some relations with antitumor activity, and a linear equation with correlation coefficient of 0.96 was found between ${\Delta}E_{{\sigma}(N-X)}(E_{{\sigma}(M-N)}-E_{{\sigma}(M-X)})$ and inhibitory activity coefficient, logIA.

• Journal of the Korean Chemical Society
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• v.27 no.4
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• pp.255-261
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• 1983

Several new $[Pd(L)X_2]$ complexes have been prepared with aminophosphines (L) such as trans-1,2-bis[diphenylphosphino)amino]cyclohexane and 1,2-bis[(diphenylphosphino) amino] propane that contain phosphorus atom as ${\pi}$-electron acceptor, and the bond character of complexes have been investigated by means of infrared and electronic spectroscopy. It was found that thiocyanate ions are N-coordinated possibly due to the steric and electronic influence of the phosphorus atom in aminophosphines that formed seven-membered chelate rings, and that spectrochemical series that is derived from the electronic spectra of the complexes is $NCS^- > Cl^- > Br^- > I^-$

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.685-691
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• 1992

The $d^8$-transition metal complexes containing diphosphine, $MCl_2PP$ were prepared by using $K_nMCl_m$ as starting materials, wherein M were Ni(II), Pd(II), Pt(II) and Au(III) and PP were bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)ethane(dppe), bis(diphenylphosphino)propane (dppp) and bis(diphenylphosphino)ethylene(dppety). The complexes were characterized by the spectral property $(^H-NMR$, $^{31}P-NMR$ and UV-Visible spectra) together with elemental analysis. The complexes were tested for the catalytic activity on the formation reactions of 3(2H)-furanone and cyclic carbonate. The only Ni(II)- and Pd(II)-diphosphine complexes displayed a good catalytic effects in the production of 3(2H)-furanone from 2-methyl-3-butyn-2-ol [reaction (1)]. But all the diphosphine complexes as catalyst were almost inactive towards cyclic carbonate production preaction [reaction (2)].