Samarium(II) Monoalkyl Complex Supported by a β‐Diketiminato‐Based Tetradentate Ligand: Synthesis, Structure, and Catalytic Hydrosilylation of Internal Alkynes

作者：Xiaojuan Liu, Qingqing Wen, Li Xiang, Xuebing Leng, Yaofeng Chen · 发表于：Chemistry - A European Journal · 年份：2020 · DOI：10.1002/chem.202000342 · 被引用次数：21 · 研究领域：Organoboron and organosilicon chemistry、Organometallic Complex Synthesis and Catalysis、Catalytic Cross-Coupling Reactions

Abstract The synthesis and catalytic applications of trivalent rare‐earth metal alkyl complexes have been well developed, but the chemistry of divalent rare‐earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β‐diketiminato‐based tetradentate ligand, [LSmCH(SiMe 3 ) 2 ] (L=[MeC(NDipp)CHC(Me)NCH 2 CH 2 N(Me)CH 2 CH 2 NMe 2 ] − , Dipp=2,6‐( i Pr) 2 C 6 H 3 ). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm( μ ‐I)] 2 and KCH(SiMe 3 ) 2 in 63 % yield. Its structure is characterized by single‐crystal X‐ray diffraction, showing a distorted square‐pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl‐substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α‐( E ) products in high yields.