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

Data for paper published in <i>Inorganic Chemistry</i> (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.<br><br>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(<b>1</b>_{<strong>M</strong>}, M = Y, Gd, Tb, Dy) reduce hexaazatrinaphthylene and its hexamethyl derivative to give trimetallic, where the [R₆HAN]^3– ligands (R = H, <b>2</b>_{<strong>M</strong>}; R = Me, <b>3</b>_{<strong>M</strong>}) form with <i>S</i> = 1/2, and with elimination of N₂. The structures of <b>2</b>_{<strong>M</strong>} and <b>3</b>_{<strong>M</strong>} reveal that the <i>tert</i>-butyl substituents strongly influence the core geometry of these trimetallic complexes. Analysis of the magnetism and electronic structure of <b>2</b>_{<strong>Gd</strong>} and <b>3</b>_{<strong>Gd</strong>} identifies ferromagnetic metal-radical exchange, with coupling constants of <i>J</i> = +2.87 cm^–1 and +3.07 cm^–1, respectively (–2<i>J</i> formalism). The unusual ferromagnetic exchange is a consequence of charge transfer to the gadolinium 5d, 6s and 6p orbitals from the radical ligands.