Donor-Acceptor Stabilized Tetra(silanimine)

Yu Liang Shan; Bi Xiang Leong; Yongxin Li; Rakesh Ganguly; Cheuk Wai So

doi:10.1021/acs.inorgchem.6b02727

Donor-Acceptor Stabilized Tetra(silanimine)

Yu Liang Shan, Bi Xiang Leong, Yongxin Li, Rakesh Ganguly, Cheuk Wai So^*

^*Corresponding author for this work

Nanyang Technological University

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	1609-1615
Number of pages	7
Journal	Inorganic Chemistry
Volume	56
Issue number	3
DOIs	https://doi.org/10.1021/acs.inorgchem.6b02727
Publication status	Published - Feb 6 2017
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.6b02727

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title = "Donor-Acceptor Stabilized Tetra(silanimine)",

abstract = "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.",

author = "Shan, {Yu Liang} and Leong, {Bi Xiang} and Yongxin Li and Rakesh Ganguly and So, {Cheuk Wai}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.6b02727",

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T1 - Donor-Acceptor Stabilized Tetra(silanimine)

AU - Shan, Yu Liang

AU - Leong, Bi Xiang

AU - Li, Yongxin

AU - Ganguly, Rakesh

AU - So, Cheuk Wai

PY - 2017/2/6

Y1 - 2017/2/6

N2 - 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.

AB - 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.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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ER -

Donor-Acceptor Stabilized Tetra(silanimine)

Abstract

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