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

Autor: Sharutin, V. V., Senchurin, V. S.
Předmět:
Zdroj: Russian Journal of Coordination Chemistry; Jul2023, Vol. 49 Issue 7, p453-457, 5p
Abstrakt: 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 [PdHal3(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)°−110.31(7)°) and CSbC (100.03(16)°−117.62(15)°) bond angles slightly differed from the theoretical value and close P−C (1.7903(15)−1.8037(16) Å) and Sb−C (2.061(5)−2.100(4) Å) bond lengths. The P−CAlk bonds are longer (1.8037(16) Å) than the P−CPh bonds. In the square planar anions [PdHal3(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) Å, respectively, and the S−Pd distances (2.2492(6) and 2.237(2) Å) are less than the sum of covalent radii of palladium and sulfur atoms (2.44 Å). The cis-ClPdCl (89.88(3)°) and cis-BrPdBr (88.93(4)°, 89.59(4)°) angles do not almost differ from the theoretical value (90°). The trans-ClPdCl and trans-SPdCl angles are comparable and equal to 178.15(2)° and 178.714(19)°. The corresponding values for complex II are 174.22(3)° and 177.53(4)°. The deviations of the palladium atom from the Cl3S and Br3S planes are insignificant (0.019 and 0.033 Å). The structural organization in the crystals of the complexes is formed by interionic contacts S=O···H–C (2.56−2.72 Å (I) and 2.44−2.62 Å (II)), Pd–Cl···H–C (2.83−2.93 Å), and Br···H (2.86−3.04 Å). [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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