Donor-acceptor stabilized tetra(silanimine)

The synthesis of an oligo(silanimine) is described. The reaction of the amidinato silylene [LSiN(SiMe3)2] (1, L = PhC(NtBu)2) with SiI4 in toluene afforded a mixture of the silanimine [LSi(I)NSiI3] (2), SiMe3I, and Si2I6. The mechanistic studies showed that 1 reacts with SiI4 to form the silyl ionic...

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Main Authors: Shan, Yu-Liang, Leong, Bi-Xiang, Li, Yongxin, Ganguly, Rakesh, So, Cheuk-Wai
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2020
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Online Access:https://hdl.handle.net/10356/139458
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Institution: Nanyang Technological University
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spelling sg-ntu-dr.10356-1394582023-02-28T19:21:48Z Donor-acceptor stabilized tetra(silanimine) Shan, Yu-Liang Leong, Bi-Xiang Li, Yongxin Ganguly, Rakesh So, Cheuk-Wai School of Physical and Mathematical Sciences Science::Chemistry Mixtures Hydrocarbons The synthesis of an oligo(silanimine) is described. The reaction of the amidinato silylene [LSiN(SiMe3)2] (1, L = PhC(NtBu)2) with SiI4 in toluene afforded a mixture of the silanimine [LSi(I)NSiI3] (2), SiMe3I, and Si2I6. The mechanistic studies showed that 1 reacts with SiI4 to form the silyl ionic intermediate "{LSi(I)N(SiMe3)2}+{SiI3}-", which then eliminates SiMe3I and "SiI2" to form the silanimine intermediate "LSi(I)NSiMe3". It further undergoes a substitution with another molecule of SiI4 to form a mixture of 2 and SiMe3I. In addition, "SiI2" undergoes an oxidative addition with SiI4 to form Si2I6. Subsequently, compound 2 reacted with [LiN(SiMe3)Ar] to form the silanimine [LSi(I)NSiI2N(SiMe3)Ar] (6, Ar = 2,6-iPr2C6H3), which was then treated with KC8 to give the donor-acceptor stabilized tetra(silanimine) [LSiN(SiMe3)SiNAr]2 (7). It comprises four formal silanimine ">Si═N-" units, which are linked together. Compounds 2, 6, and 7 were characterized by NMR spectroscopy and X-ray crystallography. ASTAR (Agency for Sci., Tech. and Research, S’pore) Accepted version 2020-05-19T09:12:34Z 2020-05-19T09:12:34Z 2017 Journal Article Shan, Y.-L., Leong, B.-X., Li, Y., Ganguly, R., & So, C.-W. (2017). Donor-acceptor stabilized tetra(silanimine). Inorganic chemistry, 56(3), 1609–1615. doi:10.1021/acs.inorgchem.6b02727 0020-1669 https://hdl.handle.net/10356/139458 10.1021/acs.inorgchem.6b02727 28094934 2-s2.0-85011841805 3 56 1609 1615 en Inorganic chemistry This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.6b02727. application/pdf
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Science::Chemistry
Mixtures
Hydrocarbons
spellingShingle Science::Chemistry
Mixtures
Hydrocarbons
Shan, Yu-Liang
Leong, Bi-Xiang
Li, Yongxin
Ganguly, Rakesh
So, Cheuk-Wai
Donor-acceptor stabilized tetra(silanimine)
description The synthesis of an oligo(silanimine) is described. The reaction of the amidinato silylene [LSiN(SiMe3)2] (1, L = PhC(NtBu)2) with SiI4 in toluene afforded a mixture of the silanimine [LSi(I)NSiI3] (2), SiMe3I, and Si2I6. The mechanistic studies showed that 1 reacts with SiI4 to form the silyl ionic intermediate "{LSi(I)N(SiMe3)2}+{SiI3}-", which then eliminates SiMe3I and "SiI2" to form the silanimine intermediate "LSi(I)NSiMe3". It further undergoes a substitution with another molecule of SiI4 to form a mixture of 2 and SiMe3I. In addition, "SiI2" undergoes an oxidative addition with SiI4 to form Si2I6. Subsequently, compound 2 reacted with [LiN(SiMe3)Ar] to form the silanimine [LSi(I)NSiI2N(SiMe3)Ar] (6, Ar = 2,6-iPr2C6H3), which was then treated with KC8 to give the donor-acceptor stabilized tetra(silanimine) [LSiN(SiMe3)SiNAr]2 (7). It comprises four formal silanimine ">Si═N-" units, which are linked together. Compounds 2, 6, and 7 were characterized by NMR spectroscopy and X-ray crystallography.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Shan, Yu-Liang
Leong, Bi-Xiang
Li, Yongxin
Ganguly, Rakesh
So, Cheuk-Wai
format Article
author Shan, Yu-Liang
Leong, Bi-Xiang
Li, Yongxin
Ganguly, Rakesh
So, Cheuk-Wai
author_sort Shan, Yu-Liang
title Donor-acceptor stabilized tetra(silanimine)
title_short Donor-acceptor stabilized tetra(silanimine)
title_full Donor-acceptor stabilized tetra(silanimine)
title_fullStr Donor-acceptor stabilized tetra(silanimine)
title_full_unstemmed Donor-acceptor stabilized tetra(silanimine)
title_sort donor-acceptor stabilized tetra(silanimine)
publishDate 2020
url https://hdl.handle.net/10356/139458
_version_ 1759856453320966144