Data for paper: Reduction of Hexaazatrinaphthylenes by Masked Divalent Lanthanide Dinitrogen Reagents

Data for paper published in Inorganic Chemistry (June 25, 2025)X-ray crystallography data in .cif format.checkCIF files for X-ray crystallography data in .pdf format.EPR spectroscopy data.IR spectroscopy data.magnetic measurement data.AbstractThe oxidation state +2 is of interest in rare-earth chemistry since it allows these conventionally redox-inactive metals to be used as reducing agents. However, the divalent oxidation state is difficult to form for most rare-earth elements, and the ensuing compounds are often unstable. Here, we describe an approach to rare-earth reduction chemistry that circumvents the divalent oxidation state by using compounds of trivalent rare earths that store reducing electrons on the dinitrogen ligand [N2]2–, akin to ‘masked’ divalent reactivity. Thus, the dinitrogen complexes(1M, M = Y, Gd, Tb, Dy) reduce hexaazatrinaphthylene and its hexamethyl derivative to give trimetallic, where the [R6HAN]3– ligands (R = H, 2M; R = Me, 3M) form with S = 1/2, and with elimination of N2. The structures of 2M and 3M reveal that the tert-butyl substituents strongly influence the core geometry of these trimetallic complexes. Analysis of the magnetism and electronic structure of 2Gd and 3Gd identifies ferromagnetic metal-radical exchange, with coupling constants of J = +2.87 cm–1 and +3.07 cm–1, respectively (–2J formalism). The unusual ferromagnetic exchange is a consequence of charge transfer to the gadolinium 5d, 6s and 6p orbitals from the radical ligands.