Palladium Complexes [Ph3PCH2C(O)Me][PdCDmso-S)] and [Ph4Sb(Dmso-O)][PdBr3(Dmso-S)]: Synthesis and Structures

Ionic palladium complexes with mononuclear anions [Ph3PCH2C(O)Me][PdCl3(Dmso-S)] (I) and [Ph4Sb(Dmso-O)][PdBr3(Dmso-S)] (II) are synthesized from tetraorganylphosphonium or tetraorganylstibonium halide and palladium dihalide in the presence of hydrochloric or hydrobromic acid. The structures of complexes I and II are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 1907718 (I) and 1979208 (II)). The complexes contain tetrahedral tetraorganylphosphonium or tetraorganylstibonium cations and square anions [PdHal(3)(Dmso-S)](-). According to the XRD data, the phosphorus and antimony atoms in the cations have a slightly distorted tetrahedral coordination with the CPC (105.76(7)& DEG;-110.31(7)& DEG;) and CSbC (100.03(16)& DEG;-117.62(15)& DEG;) bond angles slightly differed from the theoretical value and close P-C (1.7903(15)-1.8037(16) & ANGS;) and Sb-C (2.061(5)-2.100(4) & ANGS;) bond lengths. The P-C-Alk bonds are longer (1.8037(16) & ANGS;) than the P-C-Ph bonds. In the square planar anions [PdHal(3)(Dmso-S)](-), the Pd-Cl and Pd-Br bond lengths vary in ranges of 2.2918(7)-2.3012(8) and 2.371(3)-2.403(2) & ANGS;, respectively, and the S-Pd distances (2.2492(6) and 2.237(2) & ANGS;) are less than the sum of covalent radii of palladium and sulfur atoms (2.44 & ANGS;). The cis-ClPdCl (89.88(3)& DEG;) and cis-BrPdBr (88.93(4)& DEG;, 89.59(4)& DEG;) angles do not almost differ from the theoretical value (90 & DEG;). The trans-ClPdCl and trans-SPdCl angles are comparable and equal to 178.15(2)& DEG; and 178.714(19)& DEG;. The corresponding values for complex II are 174.22(3)& DEG; and 177.53(4)& DEG;. The deviations of the palladium atom from the Cl3S and Br3S planes are insignificant (0.019 and 0.033 & ANGS;). The structural organization in the crystals of the complexes is formed by interionic contacts S=O & BULL;& BULL;& BULL;H-C (2.56-2.72 & ANGS; (I) and 2.44-2.62 & ANGS; (II)), Pd-Cl & BULL;& BULL;& BULL;H-C (2.83-2.93 & ANGS;), and Br & BULL;& BULL;& BULL;H (2.86-3.04 & ANGS;).