This grant in Organic and Macromolecular Chemistry provides support for the research of Dr. Maitland Jones, Jr., Princeton University. The work focuses on the properties of carbon species which lack the usual full complement of electrons. Such species, called carbenes, have both unusual physical and chemical properties. An understanding of their behavior is important as they are found to be intermediates in a variety of chemical reactions. The spectroscopy and chemistry of substituted adamantylcarbenes will be investigated as will the study of gas phase reactions of polycarbenes. A new synthesis of one class of bridgehead double bond-containing compounds will also be sought as will other new sources and reactions of polycarbenes. A newly discovered photochemical source of dihalocarbenes will be used to continue the investigation of reports of non-sterospecific singlet carbene additions, and to see if the photochemically generated species differ in properties from the more conventionally produced intermediates. The new route will be expanded into a general method for generating divalent carbon. New compounds containing bridgehead double bonds which are kinetically stabilized by adamantyl blocking groups will be synthesized, as will a new class of bridgehead double bond containing molecules that benefit little from pyramidalization. Both the intermolecular and intramolecular reactions of carbenes with carboranes will be studied. In the latter case, new carbon-boron bridged intermediates have been produced, and these will be used to study the effect of neighboring frameworks of carbon and boron on reactive intermediates. The first carbene alpha to boron will be synthesized and investigated. An attempt will be made to synthesize both C-C and C-B carborynes.
