Kinetic Solvent Effects on the Reaction of an Aromatic Ketone π,π* Triplet with Phenol. Rate-Retarding and Rate-Accelerating Effects of Hydrogen-Bond Acceptor Solvents

Abstract

Quenching of the 2-benzoylthiophene π,π* triplet, 3BT*, by phenol yields the corresponding ketyl and phenoxyl radicals. Reaction rates were measured in 10 solvents having a range of hydrogen-bond acceptor strengths (β2H values). There appear to be two mechanisms: (i) a bimolecular reaction of 3BT* with “free” (i.e., not H-bonded) phenol in which the 3BT* accepts both a proton and an electron from the phenol, the rate decreasing as β2H increases; (ii) a trimolecular reaction of 3BT* with phenol that is H-bonded to a solvent molecule, PhO−H···S, in which the proton goes to the S and the electron to the 3BT*, the rate increasing as β2H increases.