Trisyl-based multidentate ligands: synthesis and their transition-metal complexes

Abstract

Herein we report the synthesis and applications of unusual trisyl-based multidentate ligands [trisyl = tris(trimethylsilyl)methyl, –C(SiMe₃)₃]. First, by applying a new trisyl synthon (Me₃Si)₂CH(SiMe₂CH₂Cl) 1, trisyl-based S- or N-containing compounds 2 were efficiently obtained. On treatment of these compounds 2 with MeLi, their corresponding S- or N-coordinated pincer-like trisyl-based lithium salts 3, including the S-bridged ditrisyl compound 3a [Li{C(SiMe₃)₂SiMe₂CH₂SCH₂SiMe₂C(SiMe₃)₂}Li(DME)₃] and the N-coordinated monotrisyl compounds 3b [(NacNac^DippLiCH₂SiMe₂C(SiMe₃)₂Li(THF)], 3c [Li(THF){C(SiMe₃)₂SiMe₂CH₂N(Me)CH₂C₅H₄N-2}], and 3d [Li{C(SiMe₃)₂SiMe₂CH₂N(Me)CH₂CH₂N(ⁱPr)₂}] were synthesized and structurally characterized by single-crystal X-ray structural analysis. Second, to test these novel lithium salts as straightforward precursors for the synthesis of transition-metal complexes with unique structures, these lithium salts were applied to react with MCl₂ (M = Cr, Mn, Fe, Co). Their corresponding transition-metal complexes 4–8 were obtained in high yields and structurally characterized by single-crystal X-ray structural analysis. Third, the preliminary reactivities of compound 4 were explored.