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Hypercoordinated Oligosilanes Based on Aminotrisphenols.

ACS Omega 2018 August 32
The hypercoordinated silicon chlorides ClSi[( o -OC6 H4 )3 N] ( 3 ) and ClSi[(OC6 H2 Me2 CH2 )3 N] ( 5 ) were used for the synthesis of catenated derivatives (Me3 Si)3 SiSi[( o -OC6 H4 )3 N] ( 9 ), (Me3 Si)3 SiSiMe2 SiMe2 Si(SiMe3 )2 Si[( o -OC6 H4 )3 N] ( 11 ), and (Me3 Si)3 SiSi[(OC6 H2 Me2 CH2 )3 N] ( 13 ) in reactions with (Me3 Si)3 SiK·THF ( 7 ) or (Me3 Si)3 SiK·[18-crown-6] ( 8 ). It was found that the nature of the (Me3 Si)3 SiK solvate determines the product of interaction, resulting in the formation of (Me3 Si)3 Si(CH2 )4 OSi[(OC6 H2 Me2 CH2 )3 N] ( 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(CH2 C6 H2 Me2 O)3 Si]2 O ( 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.

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