Theoretical study on the formation of silacyclopropene from acylsilane and acetylene via silene-to-silylene rearrangement

Hiromasa Tanaka, Yoshiyuki Kondo, Yoshihito Shiota, Akinobu Naka, Mitsuo Ishikawa, Kazunari Yoshizawa

研究成果: ジャーナルへの寄稿記事

6 引用 (Scopus)

抄録

Density functional theory calculations have been performed for a proposal of possible mechanisms of the thermal reaction of an acylsilane, pivaloyltris- (trimethylsilyl)silane, and bis(trimethylsilyl)acetylene yielding a silacyclopropene, 1-[(tertbutyl) bis(trimethylsilyl)methyl]-1-trimethylsiloxy-2, 3-bis(trimethylsilyl)-1-silacycloprop-2-ene. Two reaction pathways in which two different silyl species play a role were considered based on analogous reactions of acylsilane and alkyne: (i) A silene (SidC) intermediate derived from the acylsilane reactswith the acetylene to yield a silacyclobutene intermediate as a result of a stepwise [2 + 2] cycloaddition, and a ring-opening reaction of the silacyclobutene triggers the formation of the silacyclopropene. (ii) The silene intermediate is rearranged to a silylene intermediate, and then [2 + 1] cycloaddition of the acetylene and the silylene gives the silacyclopropene. The high activation energy calculated for the [2 + 2] cycloaddition indicates that the silene would not react with the acetylene, which is consistent with the experimental result that no silacyclobutene intermediate was observed. On the other hand, the second reaction pathway involving the silene-to-silylene rearrangement and the [2 + 1] cycloaddition is more realistic from thermodynamic and kinetic points of view. All the calculated results strongly suggest that the silyl species reacting with bis- (trimethylsilyl)acetylene is not silene but silylene.

元の言語英語
ページ(範囲)3160-3167
ページ数8
ジャーナルOrganometallics
30
発行部数11
DOI
出版物ステータス出版済み - 5 17 2011

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Acetylene
acetylene
Cycloaddition
cycloaddition
Silanes
Alkynes
alkynes
silanes
Density functional theory
proposals
Activation energy
actuators
Thermodynamics
activation energy
density functional theory
thermodynamics
Kinetics
rings
kinetics

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

これを引用

Theoretical study on the formation of silacyclopropene from acylsilane and acetylene via silene-to-silylene rearrangement. / Tanaka, Hiromasa; Kondo, Yoshiyuki; Shiota, Yoshihito; Naka, Akinobu; Ishikawa, Mitsuo; Yoshizawa, Kazunari.

:: Organometallics, 巻 30, 番号 11, 17.05.2011, p. 3160-3167.

研究成果: ジャーナルへの寄稿記事

Tanaka, Hiromasa ; Kondo, Yoshiyuki ; Shiota, Yoshihito ; Naka, Akinobu ; Ishikawa, Mitsuo ; Yoshizawa, Kazunari. / Theoretical study on the formation of silacyclopropene from acylsilane and acetylene via silene-to-silylene rearrangement. :: Organometallics. 2011 ; 巻 30, 番号 11. pp. 3160-3167.
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abstract = "Density functional theory calculations have been performed for a proposal of possible mechanisms of the thermal reaction of an acylsilane, pivaloyltris- (trimethylsilyl)silane, and bis(trimethylsilyl)acetylene yielding a silacyclopropene, 1-[(tertbutyl) bis(trimethylsilyl)methyl]-1-trimethylsiloxy-2, 3-bis(trimethylsilyl)-1-silacycloprop-2-ene. Two reaction pathways in which two different silyl species play a role were considered based on analogous reactions of acylsilane and alkyne: (i) A silene (SidC) intermediate derived from the acylsilane reactswith the acetylene to yield a silacyclobutene intermediate as a result of a stepwise [2 + 2] cycloaddition, and a ring-opening reaction of the silacyclobutene triggers the formation of the silacyclopropene. (ii) The silene intermediate is rearranged to a silylene intermediate, and then [2 + 1] cycloaddition of the acetylene and the silylene gives the silacyclopropene. The high activation energy calculated for the [2 + 2] cycloaddition indicates that the silene would not react with the acetylene, which is consistent with the experimental result that no silacyclobutene intermediate was observed. On the other hand, the second reaction pathway involving the silene-to-silylene rearrangement and the [2 + 1] cycloaddition is more realistic from thermodynamic and kinetic points of view. All the calculated results strongly suggest that the silyl species reacting with bis- (trimethylsilyl)acetylene is not silene but silylene.",
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T1 - Theoretical study on the formation of silacyclopropene from acylsilane and acetylene via silene-to-silylene rearrangement

AU - Tanaka, Hiromasa

AU - Kondo, Yoshiyuki

AU - Shiota, Yoshihito

AU - Naka, Akinobu

AU - Ishikawa, Mitsuo

AU - Yoshizawa, Kazunari

PY - 2011/5/17

Y1 - 2011/5/17

N2 - Density functional theory calculations have been performed for a proposal of possible mechanisms of the thermal reaction of an acylsilane, pivaloyltris- (trimethylsilyl)silane, and bis(trimethylsilyl)acetylene yielding a silacyclopropene, 1-[(tertbutyl) bis(trimethylsilyl)methyl]-1-trimethylsiloxy-2, 3-bis(trimethylsilyl)-1-silacycloprop-2-ene. Two reaction pathways in which two different silyl species play a role were considered based on analogous reactions of acylsilane and alkyne: (i) A silene (SidC) intermediate derived from the acylsilane reactswith the acetylene to yield a silacyclobutene intermediate as a result of a stepwise [2 + 2] cycloaddition, and a ring-opening reaction of the silacyclobutene triggers the formation of the silacyclopropene. (ii) The silene intermediate is rearranged to a silylene intermediate, and then [2 + 1] cycloaddition of the acetylene and the silylene gives the silacyclopropene. The high activation energy calculated for the [2 + 2] cycloaddition indicates that the silene would not react with the acetylene, which is consistent with the experimental result that no silacyclobutene intermediate was observed. On the other hand, the second reaction pathway involving the silene-to-silylene rearrangement and the [2 + 1] cycloaddition is more realistic from thermodynamic and kinetic points of view. All the calculated results strongly suggest that the silyl species reacting with bis- (trimethylsilyl)acetylene is not silene but silylene.

AB - Density functional theory calculations have been performed for a proposal of possible mechanisms of the thermal reaction of an acylsilane, pivaloyltris- (trimethylsilyl)silane, and bis(trimethylsilyl)acetylene yielding a silacyclopropene, 1-[(tertbutyl) bis(trimethylsilyl)methyl]-1-trimethylsiloxy-2, 3-bis(trimethylsilyl)-1-silacycloprop-2-ene. Two reaction pathways in which two different silyl species play a role were considered based on analogous reactions of acylsilane and alkyne: (i) A silene (SidC) intermediate derived from the acylsilane reactswith the acetylene to yield a silacyclobutene intermediate as a result of a stepwise [2 + 2] cycloaddition, and a ring-opening reaction of the silacyclobutene triggers the formation of the silacyclopropene. (ii) The silene intermediate is rearranged to a silylene intermediate, and then [2 + 1] cycloaddition of the acetylene and the silylene gives the silacyclopropene. The high activation energy calculated for the [2 + 2] cycloaddition indicates that the silene would not react with the acetylene, which is consistent with the experimental result that no silacyclobutene intermediate was observed. On the other hand, the second reaction pathway involving the silene-to-silylene rearrangement and the [2 + 1] cycloaddition is more realistic from thermodynamic and kinetic points of view. All the calculated results strongly suggest that the silyl species reacting with bis- (trimethylsilyl)acetylene is not silene but silylene.

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