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

Data for paper published in Angewandte Chemie (30.10.2025)CIF files for all compouds.check_CIF files for all compounds.EPR spectroscopy data.Magnetic measurements.NMR spectroscopy data.UV/vis spectroscopy data.AbstractA 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, 1Y; M=Dy, 1Dy; Cpttt=1,2,4-C5tBu3H2; Fp=CpFe(CO)2), where the reducing electrons originate from the bridging [Fp]− ligands. The reactivity of 1Y and 1Dy 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 1Dy is a single-molecule magnet (SMM) with an appreciable energy barrier of 449(17) cm−1, whereas [(Dy)2(μ-phnz)] (3Dy) is not an SMM because of a strong, competing equatorial crystal field. Surprisingly, [(Dy)3(HAN)] (4Dy) is also not an SMM, the origins of which are traced to the impact of the tert-butyl substituents on the dysprosium centre and its interaction with the radical [HAN]3− ligand.