Pyridines and heterocyclic thiones are among the most common nitrogen- and sulfur-donor ligands but, surprisingly, the coordination chemistry of simple bidentate ligands containing both functional groups remains largely unexplored. The (mercaptoimidazolyl)pyridine ligand mpyMe and its selenium analogue (sepyMe) have been used to prepare complexes of both transition and main group metals, including derivatives of manganese(I), nickel(II), zinc(II), cadmium(II), mercury(II), copper(I), silver(I), indium(III), tin(IV) and bismuth(III). We describe herein the synthesis and reactivity of four new mixed-donor ligands containing pyridine and mercaptoimidazole or selenoimidazole groups linked by either one or two methylene groups. More specifically, this presentation will outline the syntheses of (mercaptoimidazolyl)picoline (mpicMe), (selenoimidazolyl)picoline (sepicMe), (mercaptoimidazolyl)ethylpyridine (mepyMe) and (selenoimidazolyl)ethylpyridine (seepyMe) complexes of copper(I) and the group 12 metals, namely LCuX, LMX2, and L2HgX2 (L = mpicMe, sepicMe, mepyMe, seepyMe; M = Zn, Cd, Hg; X = Cl, Br, I), a majority of which have been structurally characterized. The preparation of homoleptic copper(I) complexes [CuL2]X (X = BF4, PF6, ClO4), which could be regarded as synthetic analogues of methanobactin, a copper-acquisition protein present in methanotrophic bacteria, will also be discussed in this presentation.

Structural effects in new pyridine-thione and pyridine-selone complexes of copper(I) and the group 12 metals

246th National Meeting (2013)

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