The ligand electronics of salen manganese nitride complexes directly influence the locus of oxidation and thus, the reactivity of the resulting oxidized species. This work investigates the influence of tert-butoxy, iso-propoxy, and methoxy substituents on the electronics of salen manganese nitride species and includes the first documentation of the para-Hammett value for the tert-butoxy substituent (σpara = -0.13 ± 0.03). Each alkoxy substituted complex undergoes metal based oxidation to form Mn(VI) and the kinetics of bimolecular homocoupling to form N2 were assessed by cyclic voltammetry. Bis-oxidation of the Mn complexes was investigated at low-temperature using cyclic voltammery and UV-vis-NIR spectroscopy, and in combination with theoretical calculations, plausible electronic structures of the di-cations are provided.
Elaboration on the Electronics of Salen Manganese Nitrides: Investigations into Alkoxy-Substituted Ligand Scaffolds
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