Time resolved spectroscopy of carbenepyridene ylides: Distinguishing carbenes from diazirine excited states

The photochemistry of diazirines and diazo compounds is not as simple as nitrogen extrusion and carbene formation. The C-H bonds adjacent to the diazo and diazirine moieties can migrate in the excited state and produce stable products without the benefit of a relaxed carbene intermediate. Additionally, cyclobutyl substituted systems exhibit carbon migration. It is unfortunate that the products of photochemical rearrangement of precursor excited states are identical to the products of thermal rearrangement of carbenes. This has prevented accurate measurement of the yield and absolute reactivity of alkylcarbenes. That pyridine reacts selectively with carbenes and not with the excited states of their nitrogenous precursors has allowed the separation of these two pathways and an appreciation of their relative importance with structural variation.