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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 29, Number 3
BKCSDE 29(3)
March 20, 2008 

Geometrical Characteristics and Reactivities of Tetracoordinated Pd Complexes: Mono- and Bidentate Ligands and Charged and Uncharged Ligands
Jin-seon Yoo, Dong-su Ha, Jae Sang Kim, Bong Gon Kim, Jong Keun Park*
Geometrical structures, Potential energy surfaces, Ligand exchange reactions, Atomic charge, Density functional theory
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), PdZ2X (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 Moller-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-π ) interactions between the dz2-orbital of Pd(II) and the π -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.
627 - 640
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