Neutral “Cp-Free” Silyl-Lanthanide(II) Complexes: Synthesis, Structure, and Bonding Analysis

[Image: see text] Complexes featuring lanthanide silicon bonds represent a research area still in its infancy. Herein, we report a series of Cp-free lanthanide (+II) complexes bearing σ-bonded silyl ligands. By reactions of LnI(2) (Ln = Yb, Eu, Sm) either with a 1,4-oligosilanyl dianion [K-Si(SiMe(3))(2)SiMe(2)SiMe(2)Si(SiMe(3))(2)-K)] (1) or with 2 (Me(3)Si)(3)SiK (3) the corresponding neutral metallacyclopentasilanes ({Me(2)Si(Me(3)Si)(2)Si}(2))Ln·(THF)(4) (Ln = Yb (2a), Eu (2b), Sm (2c)), or the disilylated complexes ({Me(3)Si}(3)Si)(2)Ln·(THF)(3) (Ln = Yb (4a), Eu (4b), Sm (4c)), were selectively obtained. Complexes 2b, 2c, 4b, and 4c represent the first examples of structurally characterized Cp-free Eu and Sm complexes with silyl ligands. In both series, a linear correlation was observed between the Ln–Si bond lengths and the covalent radii of the corresponding lanthanide metals. Density functional theory calculations were also carried out for complexes 2a–c and 4a–c to elucidate the bonding situation between the Ln(+II) centers and Si.