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

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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 ?, α = 79.453(12), β = 66.879(11), γ = 72.461(10)o, V = 998.14(9) ?3, Z = 1, Dc = 1.648 g/cm3, μ(MoKα) = 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 > 2σ(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. It crystallizes in triclinic, space group P1 with a = 10.20850 (A). The novel platinum (IV) complex [Ph3PEt] 2 [PtCl6] 1 was obtained from the reaction of H2PtCl6 and [Ph3PEt] I (Ph3PEt + = ethyl-triphenylphosphenonium) Α = 79.453 (12), β = 66.879 (11), γ = 72.461 (10) o, V = 998.14 (9) (D = 1.648 g / cm3, μ (MoKα) = 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> 2σ 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.
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