SYNTHESIS, CHARACTERIZATION AND MOLECULAR-STRUCTURES OF MONOMERIC SELENOLATO COMPLEXES OF MERCURY WITH NITROGEN-CONTAINING CHELATING LIGANDS

Intramolecularly stabilized divalent mercury selenolates of empirical formula Hg(SeR)(2) [R = 2-Me(2)NCH(2)C(6)H(4) 1, CHMeC(6)H(4)2,(R,S)-( C5H5)Fe(2-Me(2)NCHMeC(5)H(3)) 3 and (S,R)-(C5H5)Fe(2-Me(2)NCHMeC(5)H(3 )) 4] have been synthesized in high yield by treating the correspondin g diselenides with elemental mercury. The compounds show excellent sol ubility in non-polar solvents. They were characterized by elemental an alysis, H-1, C-13, Se-77 NMR, IR, Fourier-transform Raman and mass spe ctral techniques. The single-crystal structures of 1 and 4 were determ ined. Both are monomeric and the Hg atom is four-co-ordinate, being bo und to a pair of chelating aminoselenolate ligands with both the six-m embered rings having Se-Hg-N co-ordination adopting an envelope confor mation. The bond configuration about Hg in 1 can be approximated to di storted tetrahedral, while in 4 it is more square planar with the two Se atoms being mutually trans and the Se-Hg-Se angle 168.6(2)degrees. Compounds 1 and 2 vaporize without decomposition at atmospheric pressu re and decompose at higher temperatures to give HgSe while 3 decompose s to HgSe.