A Novel Platinum(Ⅳ) Halide Anion as Ethyl-triphenylphosphenonium Salt:Synthetic, Structural and Theoretical Study

摘要

A novel platinum(Ⅳ) complex [Ph3PEt]2[PtCl6] 1 obtained from the reaction of H2PtCl6 and [Ph3PEt]I (Ph3PEt+ = ethyl-triphenylphosphenonium) has been structurally characterized.It crystallizes in triclinic, space group P1 with a = 10.20850(10), b = 10.33870(10), c = 10.814 A, α =79.453(12), β = 66.879(11), γ = 72.461(10)°, V= 998.14(9) A3, Z = 1, Dc= 1.648 g/cm3, μ(MoKa) =4.025 mm-1, F(000) = 490, C40H40Cl6P2Pt, Mr = 990.44, the final R = 0.0270 and wR = 0.0617 for 5787 observed reflections with I ＞ 2o(Ⅰ). Structure analysis indicates that the platinum atom almost has the ideal octahedral coordination geometry of PtCl6. The quaternary phosphate cations (Ph3PEt+)acting as counter ions are in combination with PtCl6 anions by static attracting forces and H-bonds.Upon the hydrogen bonds existing between cations and anions, the whole structure represents a chain-like construction. Based on the crystal data, quantum chemistry calculation at the DFT/B3LPY level was carried out to reveal the electronic structure of 1.