Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes
Using Functionalized Silyl Ligands To Suppress Solvent Coordination to Silyl Lanthanide(II) Complexes
复制标题
使用功能化硅基配体抑制溶剂与硅基镧系元素 (II) 配合物的配位
作者：
R. Zitz;J. Hlina;Mohammad Aghazadeh Meshgi;H. Krenn;C. Marschner;Tibor Szilvási;J. Baumgartner
1，3-三硅烷二亚胺钾Me_2Si [Si（Me_3Si）_2K]_2与SmI_2和YbI_2反应，得到相应的二甲硅基配合物Me_2Si [Si（Me_3Si）_2]_2Sm·2 THF和Me_2Si [Si（Me_3Si）_2]_2Yb·2 THF。这些配合物中配位溶剂分子的去溶剂化使得它们的处理变得困难。然而，使用许多官能化的硅烷化物配体，获得具有减少的数目或甚至没有配位溶剂分子的络合物（（R3 Si）2Ln（THF）x（x = 0-3））。通过X射线单晶结构分析确定了所有新镧系化合物的结构。一些Yb-甲硅烷基配合物的NMR光谱分析指出，在高离子之间的相互作用的甲硅烷基配体和镧系元素。这一成键图得到了B3 PW 91/Basis 1理论水平上DFT计算的支持。详细的理论分析表明，其单占据分子轨道（SOMO）的能量非常接近的配体硅孤对（HOMO），和SQUID磁强计测量的复合物显示偏离预期的行为为一个自由的Eu（II）离子，这可能是由于配体-金属相互作用。
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.
DOI：
10.1107/s0108767394005726
发表时间：
1995-01-01
期刊：
ACTA CRYSTALLOGRAPHICA SECTION A
影响因子：
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作者：
BLESSING, RH
通讯作者：
BLESSING, RH