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Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes

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posted on 11.04.2017, 17:23 by Rainer Zitz, Johann Hlina, Mohammad Aghazadeh Meshgi, Heinz Krenn, Christoph Marschner, Tibor Szilvási, Judith Baumgartner
The reaction of the potassium 1,3-trisilanediide Me2Si­[Si­(Me3Si)2K]2 with SmI2 and YbI2 was found to give the respective disilylated complexes Me2Si­[Si­(Me3Si)2]2Sm·2THF and Me2Si­[Si­(Me3Si)2]2Yb·2THF. Desolvation of coordinated solvent molecules in these complexes made their handling difficult. However, using a number of functionalized silanide ligands, complexes with a diminished number or even no coordinated solvent molecules were obtained ((R3Si)2Ln­(THF)x (x = 0–3)). The structures of all new lanthanide compounds were determined by X-ray single-crystal structure analysis. NMR spectroscopic analysis of some Yb–silyl complexes pointed at highly ionic interactions between the silyl ligands and the lanthanides. This bonding picture was supported by DFT calculations at the B3PW91/Basis1 level of theory. Detailed theoretical analysis of a disilylated Eu­(II) complex suggests that its singly occupied molecular orbitals (SOMOs) are very close in energy to the ligand silicon lone pairs (HOMO), and SQUID magnetometry measurements of the complex showed a deviation from the expected behavior for a free Eu­(II) ion, which might be due to a ligand–metal interaction.