Relativistic DFT calculation of Sn-119 chemical shifts and coupling constants in tin compounds

The nuclear shielding and spin-spin coupling constants of Sn-119 in stannane, tetramethylstannane, methyltin halides Me4-nSnXn (X = Cl, Br, l; n = 1-3), tin halides, and some stannyl cations have been investigated computationally by DFT methods and Slater all-electron basis sets, including relativistic effects by means of the zeroth order regular approximation (ZORA) method up to spin-orbit coupling. Calculated Sn-119 chemical shifts generally correlate well with experimental values, except when several heavy halogen atoms, especially iodine, are bound to tin. In such cases, calculated chemical shifts are almost constant at the scalar (spin-free) ZORA level; only at the spin-orbit level is a good correlation, which holds for all compounds examined, attained. A remarkable '' heavy-atom effect '', analogous to that observed for analogous alkyl halides, is evident. The chemical shift of the putative stannyl cation (SnH3+) has also been examined, and it is concluded that the spectrum of the species obtained in superacids is inconsistent with a simple SnH3+ structure; strong coordination to even weak nucleophiles such as FSO3H leads to a very satisfactory agreement. On the contrary, the calculated Sn-119 chemical shift of the trimesitylstannyl cation is in very good agreement with the experimental value. Coupling constants between Sn-119 and halogen nuclei are also well-modeled in general (taking into account the large uncertainties in the experimental values); relativistic spin-orbit effects are again quite evident. Couplings to C-13 and H-1 also fall, on the average, on the same correlation line, but individual values show a significant deviation from the expected unit slope.