Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands
Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands
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DOI：
10.1021/om501123e
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发表时间：
2015-06-08
期刊：
影响因子：
2.8
通讯作者：
Mills, David P.
中科院分区：
文献类型：
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作者：
Goodwin, Conrad A. P.;Joslin, Kristian C.;Mills, David P.
硅酰胺锂[Li(Mu(3)-NHSiMe2But)](6)(1)和[Li(Mu-NHSiPr3i)(THF)](2)、(2)分别与ClSiMe3、ClSiMe2But或ClSiPr3i反应生成一系列仲硅胺。用KH去质子化得到第1族转移剂[K{Mu-N(SiMe2But)(SiMe3)/(C7H8)L(3)，[{K[Mu-N(SiPr3i)(SiMe3)]}(2)](无穷大)，(4)，[{K[Mu-N(SiMe2But)(2)]}(2)(C7H8)](无穷大)(5)，[K{N(SiPr3i)(SiMe2But})](无穷大)(6)，[KN(SIPRI)(2)}](无穷大)，(7)和[K{N(SiPr3i)(2)}(THF)(3)](8)。这些第1族转移剂与[Ln(I)(3)(THF)(4)](Ln=La，Ce)以不同的化学计量比反应生成异构体[La{N(SiMe2But)(SiMe3)}(2)(MuI)](2)(9)和同构体[Ln{N(SiMe2But)(SiMe3)}(3)]。(Ln=La 10，Ce 11)和[La{N(SiMe2But)(2)}(3)](12)。这里描述的非常大的硅酰胺配体可以赋予它们的稀土络合物不寻常的几何形状。配合物10-12在固体状态下明显表现出近似的平面性，而不是以前报道的中性同质稀土硅酰胺配合物中更常见的三角锥体形状。通过X射线结晶学、核磁共振光谱、傅立叶变换红外光谱和CHN微量分析对化合物1-12进行了不同的表征。
The lithium silylamides [Li(mu(3)-NHSiMe2But)](6) (1) and [Li(mu-NHSiPr3i)(THF)](2), (2) were reacted with ClSiMe3, ClSiMe2But, or ClSiPr3i to prepare a series of secondary silylamines by salt metathesis reactions. These were deprotonated with KH to afford the group 1 transfer agents [K{mu-N(SiMe2But)(SiMe3)/(C7H8)L (3), [{K[mu-N(SiPr3i)(SiMe3)]}(2)](infinity), (4), [{K[mu-N(SiMe2But)(2)]}(2)(C7H8)](infinity) (5), [K{N(SiPr3i)(SiMe2But}](infinity) (6), [KN(SiPri)(2)}](infinity) (7), and [K{N(SiPr3i)(2)}(THF)(3)] (8). The synthetic utility of these group 1 transfer agents has been denionstrated by their reactions with [Ln(I)(3)(THF)(4)] (Ln = La, Ce) In various stoichiometries to yield heteroleptic [La{N(SiMe2But)(SiMe3)}(2)(mu-I)](2) (9), and homoleptic [Ln{N(SiMe2But)(SiMe3)}(3)]. (Ln = La 10, Ce 11) and [La{N(SiMe2But)(2)}(3)] (12). The very-bulky silylamide ligands described herein can impart unusual geometries to their lanthanide complexes. Complexes 10-12 remarkably exhibit approximate planarity in the solid state rather than the more common trigonal pyramidal shapes, observed in previously reported neutral homoleptic lanthanide silylamide complexes. Complexes 1-12 have been variously characterized by X-ray crystallography, NMR spectroscopy, FTIR spectroscopy, and CHN microanalysis.