Divalent Ytterbium Hydrido Complex Supported by a β‑Diketiminato-Based Tetradentate Ligand: Synthesis, Structure, and Reactivity
journal contributionposted on 2021-05-17, 19:33 authored by Qingqing Wen, Bin Feng, Li Xiang, Xuebing Leng, Yaofeng Chen
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 Ph3PO, resulting in a P–CPh cleavage of Ph3PO and an elimination of C6H6; on the other hand, the reaction with Ph3PS 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.
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pyridine derivativesC 6 H 6β- diketiminato-based tetradentate ...divalent ytterbium hydridohydrido shift reaction40 yearsDivalent Ytterbium Hydrido Complexdivalent rare-earth metal hydrido c...hydrido bridge2 equivhydrido coupling-based redox reactionhydrido shiftμ- hydrogen ligandstrivalent rare-earth metal hydrido ...