Phenylnitrene computational chemistry

The transient decays at the same rate as cyclic ketenimine K is formed," implying that the newly detected transient is singlet phenylnitrene. The assignment was secured with the aid of computational chemistry" and by studying the temperature dependence of the kinetics. " In 1986 we guessed that the ISC rate constant of singlet phenylnitrene would resemble the same rate constants as those of aryl carbenes, which were known at that... 

Following the section on methylene, we present the chemistry of phenylcarbene and phenylnitrene and describe how computational chemistry helped detail why these two closely related molecules behave so differently. A discussion of tetram-ethyleneethane (TME) and oxyaUyl diradicals explores how theories of apparently simple molecules may be quite complicated. Next, we discuss the chemistry of... 

Based on their computational results, Kamey and Borden argued that an ortho substituent sterically hinders migration. When phenylnitrene is substituted at one ortho position, rearrangement occurs away from the blocked position with a barrier little different from that of phenylnitrene itself. However, when both ortho positions are occupied, the barrier for rearrangement is raised by 2-3 kcal mol , allowing for alternate reactions, especially intermolecular chemistry, to take place. 

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