Divalent Ytterbium Hydrido Complex Supported by a β‑Diketiminato-Based Tetradentate Ligand: Synthesis, Structure, and Reactivity

While the chemistry of trivalent rare-earth metal hydrido complexes has been well developed in the past 40 years, that of the divalent rare-earth metal hydrido complexes remains in its infancy because of the synthetic challenge of such complexes. In this paper, we report the synthesis and structural characterization of a divalent ytterbium hydrido complex supported by a bulky β-diketiminato-based tetradentate ligand. This hydrido complex is a dimer containing two μ-hydrogen ligands, and it easily undergoes a hydrido shift reaction to form a new divalent ytterbium hydrido complex that contains only one hydrido bridge. Furthermore, this hydrido complex reacts with pyridine and pyridine derivatives, showing versatile reactivity [Yb–H addition to pyridine, hydrido shift to ancillary ligand, and ytterbium­(II)-center-induced redox reaction with bipyridine]. This hydrido complex reacts with Ph₃PO, resulting in a P–C^Ph cleavage of Ph₃PO and an elimination of C₆H₆; on the other hand, the reaction with Ph₃PS is a hydrido coupling-based redox reaction. The reactions of this hydrido complex with 1 and 2 equiv of PhSSPh clearly indicate that the hydrido coupling-based redox reaction is prior to the ytterbium­(II) oxidation-based redox reaction.