Adventures in Reactive Intermediate Chemistry: A Perspective and Retrospective.

I review aspects of my research on reactive intermediates, specifically the physical organic chemistry of carbenes and carbocations. The topics treated include carbenoids, carbenic philicity, absolute rates of carbene/alkene additions, the diazirine exchange reaction and derived carbenes, carbene equilibria, carbocations from diazotates, and carbocations from alkoxychlorocarbenes. The essay concludes with observations on the protean nature of physical organic chemistry.