Observing Similarities and Differences in the Properties of Isostructural Niobium(V)/Tantalum(V) Coordination Compounds with Strong Pi-Donor Ligands

While niobium and tantalum are found together in their mineral ores, their respective applications in technology require chemical separation. Nb/Ta separations are challenging due to the similar reactivities displayed by these metals in the solution phase. Coordination complexes of these metals have been studied in the contexts of catalysis, small-molecule activation, and functional group insertion reactivity; relatively few studies exist directly comparing the properties of isostructural Nb/Ta complexes. Such comparisons advance the development of Nb/Ta separation chemistry through the potential for differential reactivity. Here, we explore fundamental physicochemical properties in extensively characterized Nb/Ta coordination complexes [Na(DME)3][MClamp], (Clamp6- = tris-(2-(3',5'-di-tert-butyl-2'-oxyphenyl)amidophenyl)amine; M = Nb, Ta) to advance the understanding of the different electronic, optical, and excited-state properties that these metals exhibit in pi-loaded coordination complexes.