Palladium Complexes [Ph3PC6H11-cyclo]+[PdBr3(Dmso-S)]–, [Ph3PBu]+[PdCl3(Dmso-S)]–, and [Ph3PCH2CH=CHCH2PPh3]2+[PdCl4]2–. Dmf: Synthesis and Structure

Abstract

Ph₃PC₆H11-cyclo)]⁺[PdBr₃(Dmso)]^– (I) and [Ph₃PBu]⁺[PdCl₃(Dmso)]^– (II) have been synthesized by the reactions of tetrahydrobromopalladic acid with (cyclohexyl)triphenylphosphonium bromide and tetrahydrochloropalladic acid with butyltriphenylphosphonium chloride in water with further recrystallization from dimethyl sulfoxide. [Ph₃PCH₂CH=CHCH₂PPh₃]²⁺[PdCl₄]^2–. Dmf (III) has been synthesized by a similar reaction of tetrahydrochloropalladic acid with butylene-2-bis(triphenylphosphonium) dichloride with recrystallization from N,N-dimethylformamide. According to X-ray diffraction data, P–C bond lengths and CPC angles in cations of complexes I–III variate within 1.778(2)–1.811(4) Å and 106.1(2)°–112.0(2)°, respectively. Dimethyl sulfoxide molecules in anions of complexes I and II are S-coordinated, and Pd–S bonds are 2.2478(14) and 2.2466(6) Å, while Pd–Cl distances in centrosymmetric square anions of complex III are 2.3143(5) and 2.3170(5) Å, and ClPdCl trans angles are 180°. The structural organization of crystals is formed by weak hydrogen bonds C–H...Br, C–H...Cl, and C–H...O.