The structures and reactivities of Group 12 metal complexes coordinated by tripodal nitrogen/sulfur ligands possessing internal hydrogen bond donors

Coordination compounds of nitrogen/sulfur chelate ligands are of interest to the area of bioinorganic chemistry as a means for understanding fundamental chemistry pertaining to metalloenzymes. Of particular interest is the synthesis of model compounds having relevant structural and reactivity characteristics to metal sites in biological systems. Efforts to contribute to this area have led to the development of a new family of chelate ligands that provide both nitrogen and sulfur ligand donors, as well as secondary hydrogen-bonding interactions.; The focus of the work reported herein is the synthesis, characterization, and reactivity of Zn(II), Cd(II), and Hg(II) coordination complexes of the bmnpa (N,N-bis(2-(methylthio)ethyl-N-((6-neopentylamino-2-pyridyl)methyl)amine) ligand using a variety of counter anions. This synthetic approach was undertaken in order to build a foundation upon which to develop systematic studies of structure/function relationships.; The syntheses and structures of novel nitrogen/sulfur-ligated zinc and cadmium hydroxide complexes are presented. Interesting reactivity patterns with biologically relevant substrates (e.g., formamides, esters, CO₂ ) are discussed in terms of reactive species, and primary and secondary coordination environment. The products of these reactions have been characterized and/or were independently synthesized.; 1H, 113Cd, and 199Hg NMR characterization of several cadmium and mercury compounds revealed unique and rarely observed heteronuclear coupling. 113Cd and 199Hg chemical shifts were determined as benchmarks for N/S(thioether)-ligated systems.