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-tBuC(6)H(4) (1 a)(,) 4-CH3C6H4 (1 b), Ph (1 c), 4-FC6H4 (1 d), 4-ClC6H4 (1 e), 4-CF3C6H4 (1 f)) with HF afforded the polyfluorido complexes trans-[Pt(F(HF)(2))(Ar){Ph2P(Ind)}(2)] 2 a-f, which can be converted into the fluoride derivatives trans-[Pt(F)(Ar){Ph2P(Ind)}(2)] (3 a-f) by treatment with CsF. The compounds 2 a-f and 3 a-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 2 a-f show larger |(1)J(F,Pt)|, but lower (1)J(H,F) coupling constants when compared to the fluorido complexes 3 a-f. Decreasing (1)J(P,Pt) coupling constants in 2 a-f and 3 a-f suggest a cis influence of the aryl ligands in the following order: 4-tBuC(6)H(4) (a) approximate to 4-CH3C6H4 (b)<Ph (c)MUCH LESS-THAN4-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 |(1)J(F,Pt)| coupling constants. The interpretation of the experimental data was supported by quantum-chemical DFT calculations.