palladium dibromide; phosphonium bromide; dimethylsulfoxide; diethylsulfoxide; synthesis; structure; X-ray analysis

Abstract

[Ph₃PMe]⁺[PdBr₃(dmso-S)]^– (1) and [Ph₃P(CH₂)₆PPh₃]²⁺[PdBr₃(Et₂SO-S)]^–₂ (2) was obtained by the reaction of palladium dibromide with methyltriphenylphosphonium bromide (1:1 mol.) in the dimethylsulfoxide and hexamethylene-bis-triphenylphosphonium dibromidein the diethylsulfoxide. According to X-ray analysis was performed on a Bruker D8 QUEST automatic four-circle diffractometer (Mo К_α-emission, λ = 0.71073 Å, graphite monochromator) red-brown crystals 1 [C₄₂H₄₈O₂P₂S₂Br₆Pd₂, M 1403.12, crystal system moclinic, space group P2₁, a 8.91(2), b 24.88(4), c 22.34(5) Å, V 4954(18) ų, Z 4, µ 5.747 mm^-1, independent reflections 6306, R_int 0,0525, refinement variables 1022, GOOF 1,069, R₁ = 0,0580,
wR₂ = 0.1429] and preliminary data X-rayred-brown crystals 2 [C₅₀H₆₂P₂S₂Br₆Pd₂O₂, M 1513.32, crystal system triclinic, space group P2₁, a 13.046(13), b 13.065(14), c 17.784(18) Å, V 2885(5) ų, Z 2, independent reflections 6831, R_int 0.0647, refinement variables 582, GOOF 1.086, R₁ = 0.1422, wR₂ = 0.3876] atoms P in 1 and 2 have distorted tetrahedral coordination (CPC angles 107.3(14)–111.1(14)°, 107.2(18)–110.9(16)°), bond lengths P–С 1.78(2)–1.84(3) Å and 1,77(4)–1,82(3) Å. In mononuclear planar square anions (angles SPdBr-cis 87,1(3)°, 92.8(3)° (1), 90.3(3)°, 91.0(3)° (2), BrPdBr-trance and SPdBr-trance 174.37(14)°, 177.4(2)° (1), 173.4(2)°, 178.5(3)° (2), BrPdBr-cis 89.72(19)°–90.43(19)° (1), 89.2(2)°–89.6(2)° (2)), dimethyl- and diethylsulfoxide ligands coordinated to the Pd by sulfur atoms (Pd–S 2.275(8) and 2.266(13) Å), distances Pd-Br for 1 and 2 vary in the range 2.426(5)–2.450(5) Å and 2.426(5)– 2.451(6) Å. The full tables of atomic coordinates, bond lengths, and bond angles were deposited with the Cambridge Crystallographic Data Centre (CCDC 1833574 for compound 1 deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).