Data for paper: Masked Divalent Reactivity of Heterobimetallic Lanthanide Isocarbonyl Complexes

Data for paper published in<i> </i><i>Angewandte Chemie </i>(30.10.2025)<br><br>CIF files for all compouds.<br>check_CIF files for all compounds.EPR spectroscopy data.<br>Magnetic measurements.NMR spectroscopy data.<br>UV/vis spectroscopy data.<br><br><b>Abstract</b><br>A new rare-earth reduction system is described in which trivalent yttrium and dysprosium react as though present in their unstable divalent oxidation state. This masked divalent reactivity is achieved using the isocarbonyl-bridged dimers [(M)(μ-Fp)]₂ (M=Y, <b>1</b>_{<strong>Y</strong>}; M=Dy, <b>1</b>_{<strong>Dy</strong>}; Cp^ttt=1,2,4-C₅^<em>t</em>Bu₃H₂; Fp=CpFe(CO)₂), where the reducing electrons originate from the bridging [Fp]⁻ ligands. The reactivity of <b>1</b>_{<strong>Y</strong>} and <b>1</b>_{<strong>Dy</strong>} is showcased by reducing the N-heterocycles 2,2′-bipyridyl (bipy), phenazine (phnz) and hexaazatrinaphthylene (HAN) to give corresponding mono-, di- and tri-metallic rare-earth complexes, respectively, with the heterocyclic ligands present in their singly, doubly and triply reduced forms, respectively. The dynamic magnetic properties of the dysprosium compounds are described. Compound <b>1</b>_{<strong>Dy</strong>} is a single-molecule magnet (SMM) with an appreciable energy barrier of 449(17) cm⁻¹, whereas [(Dy)₂(μ-phnz)] (<b>3</b>_{<strong>Dy</strong>}) is not an SMM because of a strong, competing equatorial crystal field. Surprisingly, [(Dy)₃(HAN)] (<b>4</b>_{<strong>Dy</strong>}) is also not an SMM, the origins of which are traced to the impact of the <i>tert</i>-butyl substituents on the dysprosium centre and its interaction with the radical [HAN]³⁻ ligand.