[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 meso -tetraarylporphyrin using [3 + 2]-cycloadditions generates meso -tetraarylhydroporphyrins. Literature evidence indicates that meso -tetraphenylporphyrins react more sluggishly with 1,3-dipoles such as ylides and OsO4 (in the presence of pyridine) than meso -tetrakis(pentafluorophenyl)porphyrin. The trend is counterintuitive for the reaction with OsO4 , 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, OsO4 , OsO4 ·py, OsO4 ·(py)2 , and ozone) with the β,β'-double bonds of variously fluorinated meso -arylporphyrins. The trend observed for the Type I cycloaddition of an ylide is straightforward, as lowering the LUMO of the porphyrin with increasing meso -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 OsO4 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.