Synthesis and Characterization of Pseudotetrahedral N(2)O and N(2)S Zinc(II) Complexes of Two Heteroscorpionate Ligands: Models for the Binding Sites of Several Zinc Metalloproteins.

Nine new pseudotetrahedral Zn(II) complexes of the heteroscorpionate ligands (3-tert-butyl-2-hydroxy(or thio)-5-methylphenyl)bis(3,5-dimethylpyrazolyl)methane, L1OH or L2SH, have been prepared and characterized (in most cases crystallographically). Complexes isolated include [(L1O)ZnCl], [(L1O)ZnI], [(L1OH)ZnI(2)], [(L1O)ZnCH(3)], [(L1O)ZnOAc], [(L1O)ZnSPh], [(L1O)ZnSBz], [(L2S)ZnCH(3)], [(L2S)ZnSPh], and [(L2S)(2)Zn]. In conjunction with the widely studied tris(pyrazolyl)borates this new series of heteroscorpionates provides a set of isolobal and isoelectronic ligands differing in donor set, i.e. N(3), N(2)O, and N(2)S. Preliminary reactivity studies with HX species, MeI, or trimethyl phosphate suggest differences between the three sets of ligands.