Aminotroponiminates: ligand-centred, reversible redox events under oxidative conditions in sodium and bismuth complexes

Abstract

A straightforward synthetic route to aminotroponate (AT) and aminotroponiminate (ATI) ligands with a ferrocenyl substituent at nitrogen is presented. Sodium derivatives have been synthesised and the first synthetic access to bismuth AT and ATI species has been demonstrated. All compounds show reversible ligand-centered redox events under oxidising conditions. In a homoleptic bismuth ATI complex, weak electronic communication between three ATI ligands was observed. The coordination chemistry and redox properties of AT and ATI compounds have been investigated by methods including NMR and UV/vis spectroscopy, single-crystal X-ray diffraction, cyclic voltammetry, and DFT calculations.