| This dissertation discusses several topics relating to the [N]phenylenes, including their behavior under flash vacuum pyrolysis conditions, and the structural characterizations of angular [4]phenylene and a metal lacycIopentadiene(alkyne) complex. A novel CpCo-shift that takes place along the linear [5]phenylene frame is also described.; Chapter one. This chapter will review synthetic routes to the [N]phenylenes. In addition, the structural, spectroscopic, and chemical properties of the phenylenes are detailed.; Chapter two. The development of methodology used to improve access angular [N]phenylenes and to synthesize the previously inaccessible unsubstituted “anti-doublebent” [5]phenylene is discussed. Several new X-ray crystal structures are presented in this chapter, including one of angular [4]phenylene and the first structurally characterized metallacyclopentadiene(alkyne) complex, a key intermediate in cobalt-mediated [2+2+2]cycloadditions.; Chapter three. The flash vacuum pyrolyses of angular [3]-, angular [4]-, and linear [3]phenylenes are described. A 13C-labeling investigation, undertaken to furthering understanding of the mechanisms that form the common (and dangerous) environmental pollutants obtained during these pyrolyses, is presented.; Chapter four. Approaches to an alkyl-solubilized linear [5]phenylene derivative and the kinetics of a novel CpCo-shift that takes place along the linear [5]phenylene frame are discussed. |
