The reaction of the Pt complexes cis-[Pt(CH 3 )(Ar)-{Ph 2 P(Ind)} 2 ] (Ind = 2-(3-methyl)indolyl, Ar = 4-tBuC 6 H 4 (1 a) , 4-CH 3 C 6 H 4 (1 b), Ph (1 c), 4-FC 6 H 4 (1 d), 4-ClC 6 H 4 (1 e), 4-CF 3 C 6 H 4 (1 f)) with HF afforded the polyfluorido complexes trans-[Pt(F(HF) 2 )(Ar){Ph 2 P(Ind)} 2 ] 2 a-f, which can be converted into the fluoride derivatives trans-[Pt(F)(Ar){Ph 2 P(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 j 1 J(F,Pt) j , 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) � 4-CH 3 C 6 H 4 (b) < Ph (c) ! 4-FC 6 H 4 (d) < 4-ClC 6 H 4 (e) < 4-CF 3 C 6 H 4 (f). In addition, the larger cis influence of aryl ligands bearing electron-withdrawing groups in the para position correlates with decreasing magnitudes of j 1 J(F,Pt) j coupling constants. The interpretation of the experimental data was supported by quantumchemical DFT calculations.