Synthesis and structure of palladium complexes [Ph3PCH2–CH=CH2]+2[PdBr4]2–, [Ph3PCH2C6H4OH-2]+2 [PdBr4]2– ∙2 DMSO and [Ph3PC6H11-cyclo]+[PdBr3(Et2SO)]–

Abstract

The interaction of palladium dibromide with allyl-, 2-hydroxybenzyl-, and cyclohexyltriphenylphosphonium bromides (2:1 mol.), followed by recrystallization of the reac-tion products from acetonitrile, dimethyl sulfoxide, and diethyl sulfoxide, respectively, has led to synthesis of complexes [Ph3PCH2–CH=CH2]2+[PdBr4]2– (1), [Ph3PCH2C6H4OH-2]2+[PdBr4]2– ∙ 2 DMSO (2), and [Ph3PC6H11-cyclo]+[PdBr3(Et2SO-S)]– (3). According to the X-ray analysis data obtained on an automatic diffractometer D8 Quest Bruker (Mo K-radiation, λ = 0.71073 Å, graphite monochromator) at 293 K, for crystals 1 [C42H40Br4P2Pd, M 1032.72, triclinic syngony, symmetry group P1; cell parameters: a = 10.19(5) Å, b = 10.35(5) Å, c = 10.90(5) Å, α = 78.1(5) degrees, β = 76.0(2) degrees, с = 75.6(2) degrees; V = 1067(9) Å3; crystal size is 0.28×0.27×0.17 mm; index ranges are 10 ≤ h ≤ 10, 10 ≤ k ≤ 10, 10 ≤ l ≤ 10; total reflections 6954; independent reflections 2198; Rint 0.0631; GOOF 1.028; R1 = 0.0648, wR2 = 0.1525; residual electron density 1.54/1.02 e/Å3], 2 [C54H56Br4O4P2PdS2, M 1321.08, orthorhombic syngony, symmetry group Pbca; cell parameters: a = 14.976(15) Å, b = 15.315(17) Å, c = 24.97(2) Å, α = β = γ = 90.00 degrees; V = 5727(10) Å3; crystal size is 0.27×0.25×0.11 mm; index ranges are 17 ≤ h ≤ 17, 16 ≤ k ≤ 16, 28 ≤ l ≤ 28; total reflections 87312; independent reflections 4238; Rint 0.0826; GOOF 1.119; R1 = 0.0475, wR2 = 0.0981; residual electron density 0.80/0.38 e/Å3], and 3 [C28H36Br3OPPdS, M 797.73, orthorhombic syngony, symmetry group Р212121; cell parameters: a = 13.534(9) Å, b = 13.547(9) Å, c = 16.907(12) Å, α = β = γ = 90.00 degrees; V = 3100(4) Å3; crystal size is 0.55×0.37×0.33 mm; index ranges are 13 ≤ h ≤ 13, 13 ≤ k ≤ 13, 17 ≤ l ≤ 17; total reflections 33931; independent reflections 3559; Rint 0.0446; GOOF 1.117; R1 = 0.0334, wR2 = 0.0783; residual electron density 0.68/0.64 e/Å3] the phosphorus atoms in cations have slightly distorted tetrahedral coordination with the CPC bond angles 106.9(7)–111.9(9) degrees, 106.1(3)–111.2(3) degrees, and 104.7(4)–113.8(4) degrees; the P–С bond lengths are 1.795(15)–1.862(18) Å, 1.767(7)–1.853(6) Å, 1.799(10)–1.802(9) Å, respectively. In the [PdBr4]2 mononuclear square planar anions of 1, 2, the BrPdBr trans- and cis-angles are 180 degrees and 88.3(4) degrees, 91.7(4) degrees, and 86.69(8) degrees, 93.31 (8) degrees; in the [PdBr3(Et2SO-S)] anion of complex 3 the BrPdBr-trans and SPdBr-trans angles are 177.29(6) degrees and 177.54(9) degrees, as distinct from the BrPdBr-cis (90.07(7) degrees, 90.15 (7) degrees), SPdBr-cis (88.26(10) degrees, 91.43(11) degrees). The Pd–Br bond lengths in 1–3 are 2.442(11), 2.463(9) Å, 2.4217(17), 2.4407(16) Å, and 2.4243(19)–2.4471(18) Å. The diethyl sulfoxide ligand in 3 is coordinated to the Pd atom via the sulfur atom; the Pd–S bond length is 2.263(3) Å. Structural organization in the crystals is caused by interionic hydrogen bonds (H∙∙∙Br 2.93–3.00 Å (1), 2.85–2.97 Å (2), 2.85–2.91 Å (3) and H∙∙∙O 2.47 Å in (3)). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1–3 are deposited at the Cambridge Structural Data Bank (No. 1990748 (1), 1898992 (2), 1898989 (3); de-posit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).