Abstract
The reactions of an overcrowded diaryldilithiosilane, Tbt(Dip)SiLi 2 (Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Dip=2,6-diisopropylphenyl), with o-dibromobenzene and 1,2,4, 5-tetrabromobenzene resulted in the synthesis and isolation of the first stable silacyclopropabenzene and bis(silacyclopropa)benzenes (IUPAC name is 4,8-disilatricyclo[5.1.0.03,5]octa-1,3(5), 6-triene), respectively. The crystallographic analyses and theoretical calculations revealed that the lengths of the juncture carbon-carbon bonds of the mono- and bis(silacyclopropa)benzenes were marginally in the range of carbon-carbon bond lengths of usual benzene rings. It is shown that this structural feature is attributable to a decrease in the strain energy of silacyclopropabenzenes relative to the corresponding cyclopropabenzenes, and the strain energy is a simple additive function of the number of the fused three-membered rings involving Si atom.
| Original language | English |
|---|---|
| Pages (from-to) | 118-126 |
| Number of pages | 9 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 686 |
| Issue number | 1-2 |
| DOIs | |
| Publication status | Published - Dec 1 2003 |
| Externally published | Yes |
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Keywords
- Bis(silacyclopropa)benzenes
- Crystallographic structural analysis
- Diaryldilithiosilane
- Silacyclopropabenzene
- Three-membered ring
ASJC Scopus subject areas
- Biochemistry
- Inorganic Chemistry
- Organic Chemistry
- Physical and Theoretical Chemistry
- Materials Chemistry
Cite this
Syntheses and structures of silicon analogues of cyclopropabenzenes. / Tajima, Tomoyuki; Hatano, Ken; Sasaki, Takayo; Sasamori, Takahiro; Takeda, Nobuhiro; Tokitoh, Norihiro; Takagi, Nozomi; Nagase, Shigeru.
In: Journal of Organometallic Chemistry, Vol. 686, No. 1-2, 01.12.2003, p. 118-126.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Syntheses and structures of silicon analogues of cyclopropabenzenes
AU - Tajima, Tomoyuki
AU - Hatano, Ken
AU - Sasaki, Takayo
AU - Sasamori, Takahiro
AU - Takeda, Nobuhiro
AU - Tokitoh, Norihiro
AU - Takagi, Nozomi
AU - Nagase, Shigeru
PY - 2003/12/1
Y1 - 2003/12/1
N2 - The reactions of an overcrowded diaryldilithiosilane, Tbt(Dip)SiLi 2 (Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Dip=2,6-diisopropylphenyl), with o-dibromobenzene and 1,2,4, 5-tetrabromobenzene resulted in the synthesis and isolation of the first stable silacyclopropabenzene and bis(silacyclopropa)benzenes (IUPAC name is 4,8-disilatricyclo[5.1.0.03,5]octa-1,3(5), 6-triene), respectively. The crystallographic analyses and theoretical calculations revealed that the lengths of the juncture carbon-carbon bonds of the mono- and bis(silacyclopropa)benzenes were marginally in the range of carbon-carbon bond lengths of usual benzene rings. It is shown that this structural feature is attributable to a decrease in the strain energy of silacyclopropabenzenes relative to the corresponding cyclopropabenzenes, and the strain energy is a simple additive function of the number of the fused three-membered rings involving Si atom.
AB - The reactions of an overcrowded diaryldilithiosilane, Tbt(Dip)SiLi 2 (Tbt=2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Dip=2,6-diisopropylphenyl), with o-dibromobenzene and 1,2,4, 5-tetrabromobenzene resulted in the synthesis and isolation of the first stable silacyclopropabenzene and bis(silacyclopropa)benzenes (IUPAC name is 4,8-disilatricyclo[5.1.0.03,5]octa-1,3(5), 6-triene), respectively. The crystallographic analyses and theoretical calculations revealed that the lengths of the juncture carbon-carbon bonds of the mono- and bis(silacyclopropa)benzenes were marginally in the range of carbon-carbon bond lengths of usual benzene rings. It is shown that this structural feature is attributable to a decrease in the strain energy of silacyclopropabenzenes relative to the corresponding cyclopropabenzenes, and the strain energy is a simple additive function of the number of the fused three-membered rings involving Si atom.
KW - Bis(silacyclopropa)benzenes
KW - Crystallographic structural analysis
KW - Diaryldilithiosilane
KW - Silacyclopropabenzene
KW - Three-membered ring
UR - http://www.scopus.com/inward/record.url?scp=0142025005&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0142025005&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(03)00446-7
DO - 10.1016/S0022-328X(03)00446-7
M3 - Article
VL - 686
SP - 118
EP - 126
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1-2
ER -