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Elaboration on the Electronics of Salen Manganese Nitrides: Investigations into Alkoxy-Substituted Ligand Scaffolds
Nicholas M Hein1, Gregory A MacNeil1, Tim Storr1
1Department of Chemistry, Simon Fraser University (SFU), 8888 University Drive, Burnaby, British Columbia V5A 1S4, Canada.
Abstract:
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, isopropoxy, 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 manganese(VI), and the kinetics of bimolecular homocoupling to form N2 were assessed by cyclic voltammetry. Bis-oxidation of the manganese complexes was investigated at low temperature using cyclic voltammery and UV-vis-near-IR spectroscopy, and in combination with theoretical calculations, plausible electronic structures of the dications are provided.
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