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Hydrogen Bonding in Platinum Indolylphosphine Polyfluorido and Fluorido Complexes

The reaction of the Pt complexes cis-[Pt(CH3)(Ar){Ph2P(Ind)}2] (Ind = 2-(3-methyl)indolyl, Ar = 4-tBuC6H4 (1a), 4-CH3C6H4 (1b), Ph (1c), 4-FC6H4 (1d), 4-ClC6H4 (1e), 4-CF3C6H4 (1f)) with HF afforded the polyfluorido complexes trans-[Pt(F(HF)2)(Ar){Ph2P(Ind)}2] 2a-f, which can be converted into the fluoride derivatives trans-[Pt(F)(Ar){Ph2P(Ind)}2] (3a-f) by treatment with CsF. The compounds 2a-f and 3a-f were characterised thoroughly by multinuclear NMR spectroscopy. The data reveal hydrogen bonding of the fluorido ligand with HF molecules and the indolylphosphine ligand. Polyfluorido complexes 2a-f show larger │1J(F,Pt)│, but lower 1J(H,F) coupling constants when compared to the fluorido complexes 3a-f. Decreasing 1J(P,Pt) coupling constants in 2a-f and 3a-f suggest a cis influence of the aryl ligands in the following order: 4-tBuC6H4 (a) ≈ 4-CH3C6H4 (b) < Ph (c) << 4-FC6H4 (d) < 4-ClC6H4 (e) < 4-CF3C6H4 (f). In addition, the larger cis influence of aryl ligands bearing electron withdrawing groups in the para position correlates with decreasing magnitudes of │1J(F,Pt)│ coupling constants The interpretation of the experimental data was supported by quantum-chemical DFT calculations.

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