Mechanistic considerations in the photodisproportionation of .mu.-oxo-bis((tetraphenylporphinato)iron(III))

Production of a Putative Iron(V)−Oxocorrole Species by Photo-Disproportionation of a Bis-Corrole−Diiron(IV)−μ-Oxo Dimer: Implication for a Green Oxidation Catalyst

“…This time-resolved spectrum for 2 and the rate of decay are essentially indistinguishable from those for the putative iron(V)-oxo corrole species formed by photolysis of chlorate complex 3 20. The photolysis of 1 had a quantum yield of 4 × 10 -4 (see Supporting Information for details), which is similar to that reported for the photolysis of a bis -porphyrin diiron(III) μ-oxo complex 8…”

Oxygen Activation Chemistry of Pacman and Hangman Porphyrin Architectures Based on Xanthene and Dibenzofuran Spacers

“…25 is believed to proceed under stereoelectronic control, which is preferred for the side-on attack of substrate on the electrophilic MÀ À À À O subunit (166)(167)(168)(169)(170)(171). To this end, the oxidative photocatalysis builds on the chemistry of unbridged PFe III À ÀOÀ ÀFe III P constructs (172)(173)(174)(175)(176)(177) with the enhancement stemming from the fact that the Pacman assembled from a single rigid pillar sterically directs substrate to the electronically preferred side-on approach to the metal-oxo bond.…”

Photochemical generation and kinetic studies of a putative porphyrin-ruthenium(v)-oxo species

“…In the presence of anthracene (10 mM), the photolysis of 2a had a quantum yield of 1.1× 10 −3 (see Experimental section for details), which is 10 times greater than that reported for the photo-disproportionation of a bis -porphyrin-diiron(III) μ-oxo complex. 31 In a slower subsequent phase of the reaction (Figure 3C), exposing photoproduct 4 to molecular oxygen led to regeneration of the bis -porphyrin-diruthenium(IV) μ-oxo complex 2a through an autooxidation pathway. 43 …”