Samarium(II) Monoalkyl Complex Supported by a β-diketiminato Based Tetradentate Ligand: Synthesis, Structure and Catalytic Hydosilylation of Internal Alkynes

Chemistry : a European Journal
Xiaojuan LiuYaofeng Chen

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 much lagged behind. Here we report the synthesis, structure and catalytic application 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 via the salt metathesis reaction of samarium iodide [LSm( µ -I)] 2 and KCH(SiMe 3 ) 2 in 63% yield. Its structure is characterized by the single-crystal X-ray diffraction, showing a distorted square pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in hydrosilylation of aryl and methyl-substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α -( E ) products in high yields.

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