Silicon-carbon unsaturated compounds. 76. Photochemical and thermal behavior of 1-silacyclobut-3-enes generated from the reaction of pivaloyltris(trimethylsilyl)silane with tert-butylacetylene

Akinobu Naka, Norihito Senba, Shingo Motoike, Hiroki Fujimoto, Toshiko Miura, Hisayoshi Kobayashi, Kazunari Yoshizawa, Mitsuo Ishikawa

研究成果: ジャーナルへの寄稿記事

9 引用 (Scopus)

抄録

Irradiation of trans-1-silacyclobut-3-ene 2, obtained by thermal isomerization of [2 + 2] cycloadduct 1 arising from the co-thermoysis of pivaloyltris(trimethylsilyl)silane with řerř-butylacetylene, with a low-pressure mercury lamp afforded an equilibrium mixture consisting of 2 and its isomer, cisl-silacyclobut-3-ene 3, in a ratio of 1:1. Similar irradiation of the cis isomer 3 gave the mixture involving equal amounts of 2 and 3. The photolysis of 2 in the presence of tert-butylalcohol gave two isomers of the cyclopropane derivative, arising from the reaction of sila bicyclobutane, A and A', with alcohol. The thermolysis of 3 at 250 °C produced 2 in quantitative yield. Similar thermolysis of 3 in the presence of tert-butylalcohol, however, afforded no alcohol adducts, but 2 was obtained as the sole product. The DFT calculations with the use of cis-2,4-dimethyl-1-siloxy-1,2-bis(silyl)-1- silacyclobut-3-ene as a starting compound and řraní-2,4-dimethyl- l-siloxy-l,2-bis(silyl)-l-silacyclobut-3ene as a product indicated that a pentacoordinate silicon intermediate plays an important role in the thermal isomerization of 3 to 2.

元の言語英語
ページ(範囲)5641-5646
ページ数6
ジャーナルOrganometallics
28
発行部数19
DOI
出版物ステータス出版済み - 10 12 2009

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Unsaturated compounds
carbon compounds
Silanes
Silicon
silanes
Isomers
Thermolysis
Carbon
isomers
Isomerization
isomerization
silicon
alcohols
Alcohols
Irradiation
Mercury vapor lamps
mercury lamps
cyclopropane
irradiation
Photolysis

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

これを引用

Silicon-carbon unsaturated compounds. 76. Photochemical and thermal behavior of 1-silacyclobut-3-enes generated from the reaction of pivaloyltris(trimethylsilyl)silane with tert-butylacetylene. / Naka, Akinobu; Senba, Norihito; Motoike, Shingo; Fujimoto, Hiroki; Miura, Toshiko; Kobayashi, Hisayoshi; Yoshizawa, Kazunari; Ishikawa, Mitsuo.

:: Organometallics, 巻 28, 番号 19, 12.10.2009, p. 5641-5646.

研究成果: ジャーナルへの寄稿記事

Naka, Akinobu ; Senba, Norihito ; Motoike, Shingo ; Fujimoto, Hiroki ; Miura, Toshiko ; Kobayashi, Hisayoshi ; Yoshizawa, Kazunari ; Ishikawa, Mitsuo. / Silicon-carbon unsaturated compounds. 76. Photochemical and thermal behavior of 1-silacyclobut-3-enes generated from the reaction of pivaloyltris(trimethylsilyl)silane with tert-butylacetylene. :: Organometallics. 2009 ; 巻 28, 番号 19. pp. 5641-5646.
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abstract = "Irradiation of trans-1-silacyclobut-3-ene 2, obtained by thermal isomerization of [2 + 2] cycloadduct 1 arising from the co-thermoysis of pivaloyltris(trimethylsilyl)silane with řerř-butylacetylene, with a low-pressure mercury lamp afforded an equilibrium mixture consisting of 2 and its isomer, cisl-silacyclobut-3-ene 3, in a ratio of 1:1. Similar irradiation of the cis isomer 3 gave the mixture involving equal amounts of 2 and 3. The photolysis of 2 in the presence of tert-butylalcohol gave two isomers of the cyclopropane derivative, arising from the reaction of sila bicyclobutane, A and A', with alcohol. The thermolysis of 3 at 250 °C produced 2 in quantitative yield. Similar thermolysis of 3 in the presence of tert-butylalcohol, however, afforded no alcohol adducts, but 2 was obtained as the sole product. The DFT calculations with the use of cis-2,4-dimethyl-1-siloxy-1,2-bis(silyl)-1- silacyclobut-3-ene as a starting compound and řran{\'i}-2,4-dimethyl- l-siloxy-l,2-bis(silyl)-l-silacyclobut-3ene as a product indicated that a pentacoordinate silicon intermediate plays an important role in the thermal isomerization of 3 to 2.",
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AU - Naka, Akinobu

AU - Senba, Norihito

AU - Motoike, Shingo

AU - Fujimoto, Hiroki

AU - Miura, Toshiko

AU - Kobayashi, Hisayoshi

AU - Yoshizawa, Kazunari

AU - Ishikawa, Mitsuo

PY - 2009/10/12

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N2 - Irradiation of trans-1-silacyclobut-3-ene 2, obtained by thermal isomerization of [2 + 2] cycloadduct 1 arising from the co-thermoysis of pivaloyltris(trimethylsilyl)silane with řerř-butylacetylene, with a low-pressure mercury lamp afforded an equilibrium mixture consisting of 2 and its isomer, cisl-silacyclobut-3-ene 3, in a ratio of 1:1. Similar irradiation of the cis isomer 3 gave the mixture involving equal amounts of 2 and 3. The photolysis of 2 in the presence of tert-butylalcohol gave two isomers of the cyclopropane derivative, arising from the reaction of sila bicyclobutane, A and A', with alcohol. The thermolysis of 3 at 250 °C produced 2 in quantitative yield. Similar thermolysis of 3 in the presence of tert-butylalcohol, however, afforded no alcohol adducts, but 2 was obtained as the sole product. The DFT calculations with the use of cis-2,4-dimethyl-1-siloxy-1,2-bis(silyl)-1- silacyclobut-3-ene as a starting compound and řraní-2,4-dimethyl- l-siloxy-l,2-bis(silyl)-l-silacyclobut-3ene as a product indicated that a pentacoordinate silicon intermediate plays an important role in the thermal isomerization of 3 to 2.

AB - Irradiation of trans-1-silacyclobut-3-ene 2, obtained by thermal isomerization of [2 + 2] cycloadduct 1 arising from the co-thermoysis of pivaloyltris(trimethylsilyl)silane with řerř-butylacetylene, with a low-pressure mercury lamp afforded an equilibrium mixture consisting of 2 and its isomer, cisl-silacyclobut-3-ene 3, in a ratio of 1:1. Similar irradiation of the cis isomer 3 gave the mixture involving equal amounts of 2 and 3. The photolysis of 2 in the presence of tert-butylalcohol gave two isomers of the cyclopropane derivative, arising from the reaction of sila bicyclobutane, A and A', with alcohol. The thermolysis of 3 at 250 °C produced 2 in quantitative yield. Similar thermolysis of 3 in the presence of tert-butylalcohol, however, afforded no alcohol adducts, but 2 was obtained as the sole product. The DFT calculations with the use of cis-2,4-dimethyl-1-siloxy-1,2-bis(silyl)-1- silacyclobut-3-ene as a starting compound and řraní-2,4-dimethyl- l-siloxy-l,2-bis(silyl)-l-silacyclobut-3ene as a product indicated that a pentacoordinate silicon intermediate plays an important role in the thermal isomerization of 3 to 2.

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