A theoretical investigation of the remarkable nuclear spin-spin coupling pattern in [(NC)₅Pt-Tl(CN)]^-

We address the problem of the interpretation of heavy nucleus spin-spin couplings for systems being studied in solution. Solvation can create counterintuitive features concerning the spin-spin couplings, which are enhanced by relativistic effects due to the presence of heavy nuclei. This should therefore be taken into consideration for the discussion of spectra obtained from solution. Evidence for such solvent effects is provided by a relativistic density functional study of [(NC)₅Pt-Tl(CN)]^- (I). It is demonstrated that the remarkable experimentally observed spin-spin coupling pattern, e.g., ²J(Tl-C) ≫ ¹J(Tl-C) and J(Pt-Tl) ∼ 57 kHz, is semiquantitatively reproduced by our calculations if both relativistic effects and solvation are taken into account. Solvent effects are very substantial and shift the Pt-Tl coupling by more than 100%, e.g. Relativistic increase of s-orbital density at the heavy nuclei, charge donation by the solvent, and the specific features of the multicenter C-Pt-Tl-C bond are responsible for the observed coupling pattern.