Energy barriers in binding of carbon monoxide and oxygen to heme model compounds.

Binding of carbon monoxide and oxygen to sterically protected heme model compounds (basket-handle porphyrins) was investigated in liquid toluene at temperatures from 180 to 300 K by laser flash photolysis. Only a single exponential rebinding process from the solvent could be seen in the time range of 20 nsec to milliseconds. The fraction of ligands that initially escaped into the solvent decreased when the temperature was lowered, and the Arrhenius plots for the rebinding rate coefficients were found to deviate significantly from linearity. These findings suggest that protected heme model compounds might react according to a double energy-barrier scheme. In contrast, the reaction of an unprotected porphyrin can be described by a single energy barrier.