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Abstract

This thesis outlines the synthesis, characterization and coordination chemistry of new N-heterocylic benzodiazepine thione (NHT) and selone (NHSe) ligands. This new family of ligands, SBzDzArE (Ar = Xy, Mes, Dipp; E = S, Se), contain various bulky aromatic substituents on nitrogen atoms, and incorporate an aromatic ring to the backbone of the seven membered ring. In particular, closed-shell (d10) metal complexes have been synthesized in order to understand the effect of adding aromaticity to the backbone of a seven membered NHT and NHSe ligands. Several mercury(II) complexes (SBzDzArE)HgX2 (X = Cl, Br, I), silver(I) complexes [Ag(SBzDzArE)2]X (X = BF4, ClO4), and iodine adducts (SBzDzArE)I2 have been isolated and characterized by a combination of analytical and various spectroscopic techniques. Molecular structures of several mercury(II) and silver(I) complexes have been determined by X-ray crystallography, which confirms the diverse bonding nature, molecular geometry, and metal to ligand ratio of these complexes.

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