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Ligands based on the known ligand 1,2-bis(2'-pyridylethynyl)benzene, which is known to selectively bind to silver(I), were synthesized. To accomplish improved binding of silver(I), one or two side arms were attached to one of the pyridine rings on the ligand. Each side arm contained either an oxygen or nitrogen, which provides an extra "tooth" to bind to silver(I). The binding constants of the ligands to silver(I) were determined using 1H NMR spectroscopy. A silver solution was titrated into a ligand solution in DMSO-d6 at millimolar concentrations. The binding constants were calculated in two ways using the NMR titration data. The data showed the ligand with a single nitrogen containing side arm had the strongest binding to silver(I), followed by the ligand with two nitrogen containing side arms. Both of these ligands showed stronger binding to silver(I) than the unsubstituted bypyridyl ligand. The ligand with a single oxygen containing side arm showed decreased binding strength as compared to the unsubstituted bipyridyl ligand.
An investigation was undertaken of the coordinating properties of flexible tetradentate phosphorus, arsenic, and nitrogen ligands of the type D(CH2CH2CH2D')3, (where D does not = D'). A series of nickel (II) complexes with the five coordinate (Ni(ligand)X)(+) cations was isolated and studied extensively. A number of Pd(II) and Co(II) complexes were also examined. A second series of studies involved the nature of bonding in boron-transition metal complexes having groups of the type B(OCH2CH2NR2). Also, the synthesis of a number of tetradentate compounds with boron-carbon bonds was undertaken (e.g., B(Ph-AsO2)3).
Ferrocene chelating ligands provide good stability of the resulting metal complexes and redox-switchable control in chemical processes catalyzed by those complexes. In comparison to traditional di-substituted ferrocene tetradentate ligands, mono-substituted tridentate ferrocene ligands may form metal complexes with a more open coordination sphere around the metal center that may allow an increased preference for substrate coordination. In addition, a mono-substituted ferrocene ligand allows the investigation of the through bond influence of the ferrocenyl group on catalytic metal centers by increasing the metal-iron distance. In this thesis, the design, synthesis, and characterization by 1H NMR spectroscopy of a novel mono-substituted ferrocene ligand are described. To explore its ability to support metal complexes with high activity and redox-switchable in polymerization reactions, yttrium alkoxide and aluminum alkyl complexes were also synthesized and characterized by 1H NMR spectroscopy.
A modular pathway for the preparation of tetradentate ligands was developed by employment of the nitroaldol reaction (Henry-reaction). Due to the use of basic solids as catalysts, namely the hydrotalcite Syntal 696® and the anion exchange resin Amberlyst A21®, the reactions proceeded at room temperature and the products were obtained by simple work-up procedures. Furthermore, NMR investigations and single crystal X-ray diffraction revealed the stereoselectivity of the developed pathway. In the course of functional group interchanges, the employment of protecting groups was necessary. Protection with trialkylsilyl groups was easily and diastereoselectively achieved. The coordination behavior towards zinc chloride was studied as well as the catalytic activity of a custom-tailored vanadium(V) complex towards sulfoxidation. Moreover, the coordination behavior of carbonyl analogous Schiff-bases towards zinc chloride were examined. The aza-Henry reaction was deployed in the synthesis of a tetradentate diaminobutane and its coordination behavior towards zinc chloride was investigated. Several unexpected reactions, starting from N-alkylpyridylimines were observed and described.
Schiff Base Metal Complexes Schiff bases are compounds created from a condensed amino compounds, which frequently form complexes with metal ions. They have diverse applications in biology, catalysis, material science and industry. Understanding these compounds, their properties, and the available methods for synthesizing them is a key to unlocking industrial innovation. Schiff Base Metal Complexes provides a comprehensive overview of these compounds. It introduces the compounds and their properties before discussing their various synthesizing methods. A survey of existing and potential applications gives a complete picture and makes this a crucial guide for researchers and industry professionals looking to work with Schiff base complexes. Schiff Base Metal Complexes readers will also find: A systematic and organized structure designed to make information instantly accessible Detailed coverage of thermal synthesis, photochemical synthesis, and more Challenges with different methods described in order to help readers make the correct choice for their own work Schiff Base Metal Complexes is a useful reference for organic chemists, materials scientists, and researchers or industry professionals working with organometallics.