O'Brien, Julie S2013-11-072013-11-0720072007Source: Masters Abstracts International, Volume: 46-03, page: 1529.http://hdl.handle.net/10393/27543http://dx.doi.org/10.20381/ruor-18765This work focuses on the coordination and stabilization of unusual compounds and their chemistry, namely that of 1,8-diaminonaphthalene (1,8-DAN) and guanidines. Although both are bidentate ligands, 1,8-DAN is dianionic, whereas guanidines are monoanionic. As both ligands are nitrogen-based, they participate in strong interactions with their target element. The strength of chelation is enhanced by the unique pi-systems that both ligands possess. This work deals with the design of 1,8-DAN-based ligands as dianionic systems for the stabilization of main group (B, C, Ge) metals. The catalytic synthesis of guanidines, a class molecules with strong biological relevance, is presented, which is catalysed by lithium. Chapter 1 presents the background and motivation to investigate 1,8-DAN as a versatile ligand as well as the drive to synthesize guanidines by a catalytic method. Chapter 2 discusses the general design of different 1,8-DAN-based ligands by varying their pendant groups. Both symmetric and asymmetric ligands are presented. The transformation from ligands through perimidinium salts to carbenes will then be reviewed. The reason behind the existence of free carbenes versus enetetraamines for other ligands will be explained. Two interesting reactions of free carbenes will be presented and elaborated. Two different types of chelating carbenes, as well as their reactivity will follow. Finally, a metal complex of one of the free carbenes is discussed. Chapter 3 investigates the possible construction of heavier metal carbene analogues. Reasons for the illusiveness of the 1,8-DAN stabilized silylene are discussed, as well as those for the germylene. A stable borane compound is presented with two different ligand systems. Chapter 4 presents the lithium-catalyzed construction of a wide variety of guanidines from amines and carbodiimides. Reasons for their varying yields and reaction conditions are discussed. The scope of the amine substrates is expanded to heterocyclic amines and amides. Finally, the construction of propiolamidines from terminal alkynes and carbodiimides by the same catalytic route is investigated. Crystal structures which support the proposed mechanism are presented. Chapter 5 summarizes the work presented in this document and presents its final conclusions.95 p.enChemistry, Organic.Thesis