Linear, Electron-Rich, Homoleptic Rare Earth Metallocene and Its Redox Activity

The first homoleptic sandwich complex of dibenzocyclooctatetraene (dbCOT), representing a large cyclooctatetraene (COT) ligand with two fused benzene moieties, for any metal was accessed through salt metathesis of YCl₃ with K₂dbCOT in the presence of 2.2.2-cryptand. Single-crystal X-ray diffraction analysis on red-brown [K(crypt-222)][Y(dbCOT)₂], 1, revealed a remarkably linear anionic yttrocene complex featuring a centroid-yttrium-centroid angle of 180.0°. The anionic moiety adopts a pseudo D₂ geometry, where the carbon atoms of the central COT ring exhibit a staggered geometry. In total, 36 π-electrons are stored on both dbCOT anions, rendering it the largest isolated sandwich complex containing only fused aromatic rings. The solution-state structure of 1 was probed through a series of techniques involving cyclic voltammetry, UV-vis, and 1D and 2D nuclear magnetic resonance (NMR) spectroscopy, including ⁸⁹Y NMR. The density functional theory (DFT) and natural bond orbital (NBO) analysis uncovered an ionic bonding interaction between the (dbCOT)^2- ligands and Y^III ion. NICS calculations support the experimentally observed aromatic character of 1, despite the deviation from planarity found in the dbCOT moieties. The cyclic voltammograms allude to the accessibility of a radical oxidation state, dbCOT^3-•, based on a quasi-reversible feature. Excitingly, the chemical one-electron reduction of 1 through exposure to potassium graphite yielded a paramagnetic molecule, which was detected by electron paramagnetic resonance (EPR) techniques. Notably, this EPR spectrum is the first one for any sandwich complex containing a COT radical. Remarkably, 1 is thermally stable, and its isolation may provide access to mono- and multinuclear complexes comprising heavier metals with applications in small-molecule activation, single-molecule magnetism, and molecular nanowires.