Synthesis and structure of palladium complexes [Ph3PCH2C6H4CN-4][PdCl3(dmso-S)], [Ph3PCH2C6H4F-4]2 [Pd2Br6], and [Ph3PEt]3 [PdBr4] [Br] ∙ 2H2O

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Ionic palladium complexes with mono- and binuclear anions [Ph3PCH2C6H4CN-4][PdCl3(dmso-S)] (1), [Ph3PCH2C6H4F-4]2 [Pd2Br6] (2), and [Ph3PEt]3[PdBr4][Br] ∙ 2H2O (3) were obtained from tetraorganylphosphonium halide and palladium dihalide in the presence of hydrochloric or hydrobromic acid. The structure of these complexes was established by X-ray diffraction analysis (XRD). XRD was performed at 293 K on a D8 Quest Bruker automatic four-circle diffractometer (two-coordinate CCD detector, Mo Kα radiation, λ = 0.71073 Å, graphite monochromator). Crystallographic characteristics of crystal 1 [C28H27NOPSCl3Pd, M 669.29; monoclinic syngony, symmetry group P21; cell parameters: a = 11.297(9), b = 34.39(2), c = 12.303(9) Å; β = 91.18(3); V = 4779(6) Å3; crystal size 0.52×0.31×0.16 mm; reflection index ranges –12 ≤ h ≤ 12, –36 ≤ k ≤ 36, –13 ≤ l ≤ 13; total reflections 82462; independent reflections 12017; Rint 0.0293; GOOF 1.085; R1 = 0.0520, wR2 = 0.1473; residual electron density 2.32/0.61 e/Å3], 2 [C50H42F2P2Br6Pd2, M 1435.04; triclinic syngony, symmetry group P–1; cell parameters: a = 8.952(19), b = 16.34(4), c = 16.63(4) Å; α = 89.45(10), β = 89.70(8), γ = 83.56(16); V = 2417(9) Å3; crystal size 0.32×0.32×0.23 mm; reflection index ranges –11 ≤ h ≤ 11, –21 ≤ k ≤ 21, –21 ≤ l ≤ 21; total reflections 59198; independent reflections 10998; Rint 0.1009; GOOF 1.124; R1 = 0.1378, wR2 = 0.3138; residual electron density 1.56/1.94 e/Å3], 3 [C60H64Br5O2P3Pd, M 1415.97; orthorhombic syngony, symmetry group Pna21; cell parameters: a = 26.86(5), b = 17.39(3), c = 12.87(3) Å; α = β = γ = 90.00; V = 6012(21) Å3; crystal size 0.58×0.16×0.14 mm; reflection index ranges –35 ≤ h ≤ 36, –23 ≤ k ≤ 23, –17 ≤ l ≤ 17; total reflections 132816; independent reflections 14848; Rint 0.1346; GOOF 1.189; R1 = 0.1154, wR2 = 0.2952; residual electron density 6.84/3.24 e/Å3]. The phosphorus atoms in three crystallographically independent cations 1 have a slightly distorted tetrahedral coordination with the CPC bond angles of 106.6(8)112.1(5)°, which are little different from the theoretical value, and the close PC bond lengths [1.773(9)1.811(16) Å]. In three crystallographically independent square-planar anions [PdСl3(dmso-S)], the PdCl bond lengths vary in the ranges 2.292(3)2.318(3), while the SPd distances [2.229(6)2.261(2) Å] are less than the sum of the covalent radii of the palladium and sulfur atoms (2.44 Å). The ClPdCl cis-angles [89.27(3)90.38(3)] are practically the same as the theoretical value; the ClPdCl trans-angles [177.49(4)178.39(4)] and the SPdCl angles [174.37(4)177.71(4)] are comparable. The deviations of the palladium atoms from the Cl3S planes are insignificant and amount to 0.0640.066 Å. The structural organization in the crystal 1 is formed by the Pd–Cl∙∙∙H–C and CN∙∙∙H–C interionic contacts (2.622.95 Å and 2.542.75 Å). The geometric parameters of the cations in complexes 2 and 3 are comparable with those observed in complex 1. Crystal 2 contains two types of crystallographically independent centrosymmetric binuclear anions [Pd2Br6]2–, in which the palladium atoms are linked to each other via two μ2-bridging bromine atoms, with the PdBrbridge distances [2.433(6)2.460(6) Å] being somewhat shorter than the terminal PdBrterm bonds [2.379(6)2.399(6) Å]. The values of the PdBrbridPd and BrtermPdBrbridge bond angles in anion 2 are 85.93(13)94.12(13) and 90.44(18), 90.86(16), respectively. Crystal 3 consists of three types of crystallographically independent ethyltriphenylphosphonium cations, square tetrabromopalladate anions and bromine anions with hydrated water molecules, which structure the crystal into a whole via the Br∙∙∙H (2.783.04 Å) and Br∙∙∙O (3.264 Å) hydrogen bonds. Complete tables of atomic coordinates, bond lengths and bond angles for the structures have been deposited with the Cambridge Crystallographic Data Centre (No. 1898994 (1), No. 2115220 (2), No. 2177801 (3); deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).

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Palladium(II) complex, alkyltriphenylphosphonium cation, dimethylsulfoxido-trichloropalladate, hexabromodipalladate, tetrabromopalladate anion, bromide anion, synthesis, structure, X-ray structural studies

Короткий адрес: https://sciup.org/147251983

IDR: 147251983   |   УДК: 546.865+547.47+548.312.5   |   DOI: 10.14529/chem250306