Solid-State (199)Hg MAS NMR and Vibrational Spectroscopic Studies of Dimercury(I) Compounds

The solid-state (199)Hg MAS NMR spectra of Hg(2)X(2) (X = Cl, SCN, NCO, CH(3)CO(2), CF(3)CO(2)) have been measured, and the infrared and Raman spectra of these compounds have been recorded and analyzed to further characterize them and to assist in the interpretation of the NMR data. Spinning-sideband analysis has been used to determine the (199)Hg shielding anisotropy and asymmetry parameters Deltasigma and eta from the solid-state (199)Hg MAS NMR spectra. In contrast to the case of the corresponding mercury(II) compounds, the shielding anisotropy is found to be relatively insensitive to the nature of the X group. This is consistent with the view that the electronic environment of the Hg atom in the mercury(I) compounds is dominated by the Hg-Hg bond. The changes in the (199)Hg shielding parameters from the mercury(II) to the corresponding mercury(I) compounds, as well as the changes in these parameters in the mercury(I) compounds with changes in X, can be interpreted in terms of variations in the local paramagnetic contribution to the shielding tensor.