Tetrasilatetrahedranide: A Silicon Cage Anion

Masaaki Ichinohe; Masafumi Toyoshima; Rei Kinjo; Akira Sekiguchi

doi:10.1021/ja0305050

Tetrasilatetrahedranide: A Silicon Cage Anion

Masaaki Ichinohe, Masafumi Toyoshima, Rei Kinjo, Akira Sekiguchi^*

^*Corresponding author for this work

University of Tsukuba

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

74 Citations (Scopus)

Abstract

The first silicon cage anion, tris{bis[bis(trimethylsilyl)methyl](methyl)silyl}tetrasilatetrahedranide (6^-), has been synthesized by the reaction of tetrakis{bis[bis(trimethylsilylmethyl](methyl)silyl}tetrasilatetrahedrane with potassium graphite in diethyl ether by reductive cleavage of exocyclic Si?Si bond. The structural characterization of K⁺(18-crown-6)·6^- has been achieved by X-ray crystallography, showing that 6^- is a separated ion pair and the tetrasilatetrahedranide moiety has a significantly distorted tetrahedrane skeleton containing one inverted tetrahedral (umbrella type) silicon atom. The four silicon atoms in the Si₄ skeleton are equivalent on the NMR time scale due to the migration of the Dis2MeSi substituent.

Original language	English
Pages (from-to)	13328-13329
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	125
Issue number	44
DOIs	https://doi.org/10.1021/ja0305050
Publication status	Published - Nov 5 2003
Externally published	Yes

ASJC Scopus Subject Areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Tetrasilatetrahedranide: A Silicon Cage Anion",

abstract = "The first silicon cage anion, tris{bis[bis(trimethylsilyl)methyl](methyl)silyl}tetrasilatetrahedranide (6-), has been synthesized by the reaction of tetrakis{bis[bis(trimethylsilylmethyl](methyl)silyl}tetrasilatetrahedrane with potassium graphite in diethyl ether by reductive cleavage of exocyclic Si?Si bond. The structural characterization of K+(18-crown-6)·6- has been achieved by X-ray crystallography, showing that 6- is a separated ion pair and the tetrasilatetrahedranide moiety has a significantly distorted tetrahedrane skeleton containing one inverted tetrahedral (umbrella type) silicon atom. The four silicon atoms in the Si4 skeleton are equivalent on the NMR time scale due to the migration of the Dis2MeSi substituent.",

author = "Masaaki Ichinohe and Masafumi Toyoshima and Rei Kinjo and Akira Sekiguchi",

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TY - JOUR

T1 - Tetrasilatetrahedranide

T2 - A Silicon Cage Anion

AU - Ichinohe, Masaaki

AU - Toyoshima, Masafumi

AU - Kinjo, Rei

AU - Sekiguchi, Akira

PY - 2003/11/5

Y1 - 2003/11/5

N2 - The first silicon cage anion, tris{bis[bis(trimethylsilyl)methyl](methyl)silyl}tetrasilatetrahedranide (6-), has been synthesized by the reaction of tetrakis{bis[bis(trimethylsilylmethyl](methyl)silyl}tetrasilatetrahedrane with potassium graphite in diethyl ether by reductive cleavage of exocyclic Si?Si bond. The structural characterization of K+(18-crown-6)·6- has been achieved by X-ray crystallography, showing that 6- is a separated ion pair and the tetrasilatetrahedranide moiety has a significantly distorted tetrahedrane skeleton containing one inverted tetrahedral (umbrella type) silicon atom. The four silicon atoms in the Si4 skeleton are equivalent on the NMR time scale due to the migration of the Dis2MeSi substituent.

AB - The first silicon cage anion, tris{bis[bis(trimethylsilyl)methyl](methyl)silyl}tetrasilatetrahedranide (6-), has been synthesized by the reaction of tetrakis{bis[bis(trimethylsilylmethyl](methyl)silyl}tetrasilatetrahedrane with potassium graphite in diethyl ether by reductive cleavage of exocyclic Si?Si bond. The structural characterization of K+(18-crown-6)·6- has been achieved by X-ray crystallography, showing that 6- is a separated ion pair and the tetrasilatetrahedranide moiety has a significantly distorted tetrahedrane skeleton containing one inverted tetrahedral (umbrella type) silicon atom. The four silicon atoms in the Si4 skeleton are equivalent on the NMR time scale due to the migration of the Dis2MeSi substituent.

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ER -

Tetrasilatetrahedranide: A Silicon Cage Anion

Abstract

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