Синтез и строение гексабромоплатината циклопропилтрифенилфосфония

Abstract

Using the interaction of potassium hexabromoplatinate with cyclopropyltriphenylphosphonium bromide in acetonitrile after crystallization from dimethyl sulfoxide, the [Ph 3 PC 3 H 5 ] 2 [PtBr 6 ] complex ( 1 ) has been obtained for the first time (red crystals, m.p. 235 °C). The compound 1 has been characterized by IR-spectroscopy and X-ray analysis. According to the data of X-ray analysis the unit cell crystallographic parameters of compound 1 are: orthorhombic syngony, the symmetry group Pna2 1 ; M 1281.22; cell parameters: a = 14.653(6), b = 18.874(8), c = 15.921(8) Å; a = 90.00 degrees, β = 90.00 degrees, g = 90.00 degrees; V = 4403(3) Å 3 ; ρ (calc.) = 1.933 g/cm 3 , Z = 8, the crystal size is 0.32×0.24×0.16 mm; intervals of reflection indexes –25 ≤ h ≤ 25, –17 ≤ k ≤ 19, –21 ≤ l ≤ 20; total reflections 66507; independent disclosures 10802; μ = 8.733 mm –1 ; R 1 = 0.0344; wR 2 = 0.0755 (all date), R 1 = 0.0484; wR 2 = 0.0807 ( F 2 > 2s( F 2 )); residual electron density 1,28/–2,05 e/Å 3 . In cations, the phosphorus atoms have a distorted tetrahedral coordination (the CPC angles equal 88.6(3)°-122.4(3)°, the P-C bond lengths are 1.541(5)-2.273(7) Å). The platinum atoms are coordinated by six bromine atoms in the anion (the BrPtBr trans -angles are close to 180°, the BrPtBr cis -angles have the values 89.17(4)-108.(3)°, the Pt-Br bond lengths are 2.1618(9)-2.9732(14) Å). Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data (№ 1969775; http://www.ccdc. cam.ac.uk).