Attachment of the Bulky Bidentate Ligand C(SiMe₃)₂SiMe₂CH₂CH₂Me₂Si(Me₃Si)₂C to K, Zn, Sn, and Yb. Crystal Structures of L_nMC(SiMe₃)₂SiMe₂CH₂CH₂Me₂Si(Me₃Si)₂CML_n (ML_n = K(C₆H₆)₂, K(THF)₂, SnCl₃, or SnMe₂Cl) and CH₂SiMe₂

Abstract

6 ) 2 , 7. The structures of 7 and 8 have been confirmed by X-ray studies which indicate that both compounds show K‚‚‚Me contacts in the range 3.3-3.5 Å. The ether-free reagent 7 reacted with YbI 2 in benzene to give the cyclic Yb(II) derivative CH 2 SiMe 2 C(SiMe 3 ) 2 -YbC(SiMe 3 ) 2 SiMe 2 CH 2 , which was found to be somewhat more stable toward Et 2 O than the previously studied Yb{C(SiMe 3 ) 3 } 2 . Reaction of the lithate [Li(TMEDA) 2 ][CH 2 SiMe 2 C(SiMe 3 ) 2 -LiC(SiMe 3 ) 2 SiMe 2 CH 2 ] (2a) with ZnCl 2 in THF gave a cyclic compound CH 2 SiMe 2 C(SiMe 3 ) 2 -

Thermally Stable Ln(II) and Ca(II) Bis(benzhydryl) Complexes: Excellent Precatalysts for Intermolecular Hydrophosphination of C–C Multiple Bonds

“…σ-Bonded hydrocarbyl derivatives of divalent lanthanides, despite unique reactivity and great promise in catalysis, still remain scarce and poorly explored . Rich and diverse reactivity of these compounds is provided by the presence of two centers featuring various reactivity patterns: σ-Ln–C bond and highly reductive low valent metal.…”

Thermally Stable Half-Sandwich Benzhydryl Ln(II) (Ln = Sm, Yb) Complexes Supported by Sterically Demanding Carbazolyl and Fluorenyl Ligands

“…The impressive progress achieved in the design, synthesis, characterization, and reactivity studies of σ-bonded alkyl complexes of trivalent lanthanides was inspired by their unique reactivity and great promise in catalysis of a wide range of transformations . At the same time the hydrocarbyl derivatives of divalent lanthanides still remain poorly explored . This chemistry started recently in the early 1990s with the discovery of Yb­(II) complexes with bulky silyl-substituted ligands. − The presence of two highly reactive centers (σ-Ln–C bonds and a metal ion in a low oxidation state) provides two different patterns of rich and diverse reactivity of these alkyl species.…”

Manganese and Cesium Derivatives of the Bulky Bidentate Ligand C(SiMe3)2SiMe2CH2CH2Me2Si(Me3Si)2C. Crystal Structures of Li(THF)2.75(Et2O)0.25(μ-Cl)- MnC(SiMe3)2SiMe2CH2CH2Me2Si(Me3Si)2C and (C6H6)3CsC(SiMe3)2SiMe2CH2CH2

“…We recently reported the attachment of the bidentate “trisiamyl” ligand C(SiMe 3 ) 2 SiMe 2 CH 2 CH 2 Me 2 Si(Me 3 Si) 2 C (R−R) to Li, Hg, Pb, Zn, Yb, K, and Sn. , …”