[3 + 2]-Cycloadditions with Porphyrin β,β'-Bonds: Theoretical Basis of the Counterintuitive meso -Aryl Group Influence on the Rates of Reaction.

Removal of a β,β'-bond from -tetraarylporphyrin using [3 + 2]-cycloadditions generates -tetraarylhydroporphyrins. Literature evidence indicates that -tetraphenylporphyrins react more sluggishly with 1,3-dipoles such as ylides and OsO (in the presence of pyridine) than -tetrakis(pentafluorophenyl)porphyrin. The trend is counterintuitive for the reaction with OsO, as this formal oxidation reaction is expected to proceed more readily with more electron-rich substrates. This work presents a density functional theory-based computational study of the frontier molecular orbital (FMO) interactions and reaction profile thermodynamics involved in the reaction of archetypical cycloaddition reactions (a simple ylide, OsO, OsO·py, OsO·(py), and ozone) with the β,β'-double bonds of variously fluorinated -arylporphyrins. The trend observed for the Type I cycloaddition of an ylide is straightforward, as lowering the LUMO of the porphyrin with increasing -phenyl-fluorination also lowers the reaction barrier. The corresponding simple FMO analyses of Type III cycloadditions do not correctly model the reaction energetics. This is because increasing fluorination leads to lowering of the porphyrin HOMO-2, thus increasing the reaction barrier. However, coordination of pyridine to OsO preorganizes the transition state complex; lowering of the energy barrier by the preorganization exceeds the increase in repulsive orbital interactions, overall accelerating the cycloaddition and rationalizing the counterintuitive experimental findings.