Photochemical Production of a Highly Reactive Porphyrin−Iron−Oxo Species

Abstract

Oxidation of 5,10,15,20-tetramesitylporphyrinatoiron(III) perchlorate, (TMP)FeIII(ClO4), with ferric perchlorate in acetonitrile gave a metastable species identified as (TMP)FeIV(ClO4)2 that decayed within seconds to the known isomeric species (TMP*+)FeIII(ClO4)2. Irradiation of the metastable species with 355 nm laser light gave a highly reactive transient that reacts with simple organic reductants (alkenes and arylalkanes) 5 orders of magnitude faster than known Compound I analogues, (TMP*+)FeIV(O)(X-).