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Following the structural characterization and analysis of Blue Copper Proteins (BCP's), macrocyclic ligands have attracted much interest as simple models for naturally occurring metal-macrocycle centers. Presented in this dissertation are the syntheses and characterization of small, simple organic analogs of BCP's. Chapter I of this work gives a brief literature review of Blue Copper Proteins, including their unique spectral characteristics. The synthesis and characterization of several linear and cyclic molecular analogs will be discussed including polythiaethers,3 polyazacycloalkanes,4 thia-aza5 and trithiaethers. The macrocyclic effect will be explained and why cyclic molecular analogs are of current interest. Presented in the second chapter are the syntheses of two 14-membered rings with a 2,3,2,3 altering carbon chain arrangement for 1,8-dithia-4,11-diazacyclotetradecane and 1,11-dithia-4,8-diazacyclotetradecane. The 1,8-dithia-4,11-diazacyclotetradecane is complexed to both Cu2+ and Cu+ and fully characterized using UV-Vis, EPR and CV. The 1,11-dithia-4,8-diazacyclotetradecane was synthesized for structural X-ray comparison of the Cu2+ metal ion. The 1,8-dithia-4,11-diazacyclotetradecane having two nitrogen atoms also makes it attractive for functionalization. Presented in the third chapter of this dissertation is the expansion of these ligands for use as cryptands. The syntheses of two cryptands are fully described and include crystallographic data. One of the cryptand ligands, 1,8-dithia-4,11,18,21-tetraazatricyclo[10.6.6]pentacosane-25-one was successfully complexed to Cu2+ and those results are also discussed. To further conclude this research is a pendant arm derivative and its synthesis. Each nitrogen atom of 1,8-dithia-4,11-diazacyclotetradecane is functionalized with a four carbon chain connecting to 1,4-diaza-7-thiacyclononane.
This book describes the coordination chemistry of macrocyclic ligands. Common types of ligands are introduced and strategies for the synthesis of the free ligands and their metal complexes are discussed. The unique thermodynamic and kinetic properties of macrocyclic complexes are introduced and applications of the ligands presented. The book is suitable for advanced undergraduate or graduate students and assumes a knowledge of organic and inorganic chemistry at the second year undergraduate level.
Chemists have been aware of the existence of coordination compounds con taining organic macrocyclic ligands since the first part of this century ; however, only during the past few years have they expanded research into the chemistry of these compounds. The expansion was initiated in the early 1960s by the synthesis and characterization of compounds containing some new macrocyclic ligands. The synthesis of compounds which may serve as model systems for some natural products containing large rings as ligands provided the main goal for the early expansion of research effort; indeed, a recurrent theme behind much of the reported chemistry has been the analogy between synthetic macrocyclic compounds and many natural-product systems. More recently, the emphases of reported research have ranged over the whole spectrum of chemistry, and the number of publications that discuss macrocyclic chemistry has increased at a dramatic rate. The completed research has been reported in a variety of journals throughout the world but there has been no previous attempt to bring the major developments together under one cover. This book, therefore, attempts to satisfy the need for a single source in which there is both a collection and a correlation of information concerning the coordination chemistry of macrocyclic compounds. The chapters in this book discuss various aspects of macrocyclic chemistry, and while these chapters as a whole constitute an in-depth survey of the state-of the-art of the field, each chapter is written as a complete unit.