Hypercoordinated Oligosilanes Based on Aminotrisphenols
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资源简介：
The
hypercoordinated silicon chlorides ClSi[(o-OC6H4)3N] (3) and
ClSi[(OC6H2Me2CH2)3N] (5) were used for the synthesis of catenated
derivatives (Me3Si)3SiSi[(o-OC6H4)3N] (9), (Me3Si)3SiSiMe2SiMe2Si(SiMe3)2Si[(o-OC6H4)3N] (11), and (Me3Si)3SiSi[(OC6H2Me2CH2)3N] (13) in reactions with (Me3Si)3SiK·THF (7) or (Me3Si)3SiK·[18-crown-6] (8). It was found that the nature
of the (Me3Si)3SiK solvate determines the product
of interaction, resulting in the formation of (Me3Si)3Si(CH2)4OSi[(OC6H2Me2CH2)3N] (12) or 13. Compounds obtained were characterized using multinuclear
NMR and UV–vis spectroscopy and mass spectrometry. The molecular
structures of 3, 9, and 11–13 were investigated by single-crystal X-ray analysis, featuring
hypercoordinated Si atoms in a trigonal-bipyramidal coordination environment
with O atoms in the equatorial plane. The structure of the side product
[N(CH2C6H2Me2O)3Si]2O (6) was also studied, indicating highly
tetrahedrally distorted trigonal-bipyramidal environment at the Si
atoms, which was confirmed by crystal density functional theory calculations
indicating the very weak Si ← N interaction. The Si···N
interatomic distances span a broad range (2.23–2.78 Å).
The dependence of structural and NMR parameters for hypercoordinated
catenated compounds from the type of the ligand was established.
创建时间：
2018-08-31
