Treatment of Pd(PPh3)(4) with 5-hromo-pyrimidine [C4H3N2Br] in dichloromethane at ambient temperature cause the oxidative addition reaction to produce the palladium complex [Pd(PPh3)(2)(eta(1)-C4H3N2)(Br)], 1, by substituting two triphenylphosphine ligands. In acetonitrile solution of 1 in refluxing temperature for I day, it do not undergo displacement of the triphenylphosphine ligand to form the dipalladium complex [Pd(PPh3)Br](2){mu,eta(2)-(eta(1)-C4H3N2)}(2), or bromide ligand to form chelating pyrimidine complex [Pd(PPh3)(2)(eta(2)-C4H3N2)]Br. Complex 1 reacted with bidentate ligand, NH4S2CNC4H8, and tridentate ligand, KTp {Tp = tris(pyrazoyl-1-yl)borate}, to obtain the eta(2)-dithiocarbamate eta(1)-pyrimidine complex [Pd(PPh3)(eta(1)-C4H3N2)(eta(2)-S2CNC4H8)], 4 and eta(2)-Tp eta(1)-pyrimidine complex [Pd(PPh3)(eta(1)-C4H3N2)(eta(2)-Tp)], 5, respectively. Complexes 4 and 5 are characterized by X-ray diffraction analyses.