Se-77 solid-state NMR spectra have been recorded with cross-polarizati
on and magic-angle spinning on [M(Se4)2]2-complexes with [Me4N]+ (M =
Zn, Cd, Hg) and [Et4N]+ (M = Cd, Hg). The large chemical shift anisotr
opies (of the order of 1000 ppm) mean that fast spinning speeds (9-11
kHz) are needed in order to reveal the number of crystallographic sele
nium sites present within the solid. The spectra enable the principal
components of the Se-77 shielding tensor to be calculated from the spi
nning sideband intensities. Differences between the Se-77 isotropic ch
emical shifts observed for the [Et4N]+ complexes and for the [Me4N]+ c
omplexes reflect small structural changes in the [M(Se4)2]2- geometry
with cation. J-coupling to Hg-199 and Cd-11/113 are also observed. The
solid-state NMR results are compared with similar work in solution. A
single-crystal X-ray structure determination of [Me4N]2-[Hg(Se4)2].0.
5DMF is reported (monoclinic crystal system, space group C2/c). The Hg
atom is tetrahedrally coordinated by two chelating tetraselenide liga
nds with both HgSe4 rings adopting the envelope conformation. The FT R
aman spectrum of [Me4N]2[Cd(Se4)2] is also reported.