Synthesis and characterization of metal complexes with sulfur and nitrogen-containing ligands

This thesis describes the synthesis, characterization, and reactivity of metal complexes with sulfur and nitrogen-containing ligands. The first project focuses on ruthenium complexes that contain an η5-bound pyrrolyl ligand. For example, (NC₄H₄)RuI(PEt₃) ₂, 5, was synthesized and characterized, and the reactivity of the pyrrolyl ligand towards nucleophiles was studied. Moderately strong nucleophiles attack the C(2) position of pyrrolyl to form a ruthenium complex with a non-labile hydride. Further substitution of pyrrolyl is achieved if the hydride is converted to a labile iodide, making possible 2,5-disubstituted pyrrolyl. When compared to other pyrrolyl complexes of the general formula (NC₄H₄)RuX(PR₃)₂, it was found that the electron-donating ability of the ligands influences the reactivity of pyrrolyl, and ligands that donate more electron density result in a pyrrolyl that is more susceptible to nucleophilic attack.; The second project involved the stoichiometric reaction between the dimer (CpMoμ-S)₂S₂CH₂, 2, and one or both of the alkyne bridges in a series of dialkynes to produce a diamagnetic molybdenum(III) adducts with one molybdenum dimer (mono-adducts) and with two molybdenum dimers (di-adducts). In one instance, a monoacetylene adduct of a molybdenum dimer has been used as a ligand for a group 10 metal complex. The reaction of bis(diphenylphosphino)acetylene with (CpMoS)₂S ₂CH₂ led to the formation of an alkenedithiolate complex with terminal diphenylphosphino groups. These phosphines served as chelating sites in the formation of (CpMo)₂(S₂CH₂)(μ-S(C(P(Ph ₂)P(Ph₂)C))(μ-S))PdCl₂, 12, and its derivative (CpMo)₂(S₂CH₂)(μ-S(C(P(Ph ₂)P(Ph₂)C))(μ-S))PdMe₂, 13, a new molybdenum palladium complex which has been isolated and characterized by NMR spectroscopy, cyclic voltammetry, and single-crystal x-ray diffraction.