This grant in the Organic and Macromolecular Chemistry Program supports the research of Dr. Blair which is aimed at the preparation and study of the chemical properties of positively charged halogen complexes. Positively charged halogen atoms play a significant role in human biochemistry and they function as reagents used in the preparation of a variety of halogen-containing molecules. Despite the importance of positively charged or 2-coordinate halogen atoms, they have not been extensively investigated and they are difficult to isolate. Dr. Blair has recently circumvented these problems, characterizing such complexes by X-ray analysis. He now plans to prepare several new types of 2-coordinate halogen complexes, to examine the chemical properties of this unique type of complex and to find novel uses for these highly reactive salts. More specifically, the proposed work entails the synthesis and characterization of new 2-coordinate complexes of positive bromine and iodine and their application as new reagents. Complexes to be investigated include bis(quinuclidine)Br+ and I+ as well as the related complexes of 1,4-diazabicyclo?2.2.2! octane. Quinuclidine complexes of N-bromosuccinimide and N-iodosuccinimide will also be studied. New complexes will be characterized by X-ray crystallography, proton and carbon NMR spectroscopy, and UV-Vis spectrophotometry. The dynamics of the formation of bis(quinclidine) Br+ from the rearrangement of the dibromo quinclidine complexes will be probed by NMR and UV-Vis techniques. Refinements in the application of bis(quinclidine)Br+ as a new agent for the oxidation of alcohols will be sought to reduce costs and increase the utility of this stable and conveniently handled source of active bromine. Initial studies to determine the potential of bis(quinclidine)Br+ and I+ as new agents to introduce radio-bromine and -iodine into aromatic acids will be undertaken.
