Catalytic activity of bis p-nitro A2B (oxo)Mn(V) corroles towards oxygen transfer reaction to sulphides

Abstract The 5 A2B Mn(III) corroles have been synthesized, fully characterized and used for oxygen atom transfer (OAT) from isolated (oxo)manganese(V)corrole to sulfide. Oxidation of Mn(III) were carried out using ozone, a clean oxidant, which resulted in the isolation of the 5 red- coloured (oxo)manganese(V) corroles. The stoichiometric OAT to a different p-thioanisoles gave a mechanistic insight. The electron withdrawing and electron donating group containing phenyl group substituents on C10 meso carbon were synthesized to gain effect of substituents on the rate constant. The rate constant suggests the disproportionation reaction for OAT from (oxo)manganese(V) corrole to (oxo)manganese(IV) and (oxo)manganese(VI) corroles. Newly synthesized free bases were characterised by 1H NMR, UV–visible spectroscopy. Manganese(III) corrole, (oxo)manganese(V) corrole were characterized by UV–visible spectroscopy. Self-decay and oxygen atom transfer to sulfide rate constant were determined using UV–visible spectroscopy. Electrochemistry of these Mn(III) corroles shows the effect of meso phenyl substituents on the oxidation potential of Mn(III) corroles. DFT calculation of these synthesized Mn(III) corroles have been carried out and HOMO-LUMO gap varies with the substituents on meso carbons.