Synthesis of boron substituted stannacyclohexadienes by a competitive metathesis

Victoria Volkis; Moris S. Eisen

doi:10.1515/MGMC.1997.20.5.293

Synthesis of boron substituted stannacyclohexadienes by a competitive metathesis

Victoria Volkis, Moris S. Eisen^*

^*Corresponding author for this work

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

Abstract

The reaction of phenyl borondibromide (PhBBr₂) with 1,1-n-dibutylstanna-2,5-cyclohexadiene (8) produces, along with the expected phenylbora-2,5-cyclohexadiene (1), a mixture of boron substituted stannacyclohexadiene compounds 2 and 3 in a ratio of 1:2 respectively. Compounds 2 and 3 are in equilibrium at room temperature. The initial formation of either 2 or 3 is presumably the result of a metathesis reaction of the PhBBr₂ with the double allylic C-H bond of the starting 1,1-n-dibutylstanna-2,5-cyclohexadiene (8), yielding compound 2, or with the allylic C-H bond of the 1,3-hydrogen isomerized starting stannacycle 8 (1,1-n-dibutylstanna-2,4-cyclohexadiene), yielding compound 3. The pseudo-first order rate of conversion from 2 ⇒ 3 was measured by an NMR spin population transfer technique to be k₁ = 7.18 s^-1 (2, 0.034M; T₁ =1.6 s) while k-₁ = was found to be 3.29 s^-1 (T₁ = 1.5 s), yielding an equilibrium constant of 2.18 at 298 K. The coalescence rate constant was calculated to be 235 s^-1 which was not reached by heating the sample up to 383 K.

Original language	English
Pages (from-to)	293-299
Number of pages	7
Journal	Main Group Metal Chemistry
Volume	20
Issue number	5
DOIs	https://doi.org/10.1515/MGMC.1997.20.5.293
State	Published - 1997
Externally published	Yes

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title = "Synthesis of boron substituted stannacyclohexadienes by a competitive metathesis",

abstract = "The reaction of phenyl borondibromide (PhBBr2) with 1,1-n-dibutylstanna-2,5-cyclohexadiene (8) produces, along with the expected phenylbora-2,5-cyclohexadiene (1), a mixture of boron substituted stannacyclohexadiene compounds 2 and 3 in a ratio of 1:2 respectively. Compounds 2 and 3 are in equilibrium at room temperature. The initial formation of either 2 or 3 is presumably the result of a metathesis reaction of the PhBBr2 with the double allylic C-H bond of the starting 1,1-n-dibutylstanna-2,5-cyclohexadiene (8), yielding compound 2, or with the allylic C-H bond of the 1,3-hydrogen isomerized starting stannacycle 8 (1,1-n-dibutylstanna-2,4-cyclohexadiene), yielding compound 3. The pseudo-first order rate of conversion from 2 ⇒ 3 was measured by an NMR spin population transfer technique to be k1 = 7.18 s-1 (2, 0.034M; T1 =1.6 s) while k-1 = was found to be 3.29 s-1 (T1 = 1.5 s), yielding an equilibrium constant of 2.18 at 298 K. The coalescence rate constant was calculated to be 235 s-1 which was not reached by heating the sample up to 383 K.",

author = "Victoria Volkis and Eisen, {Moris S.}",

year = "1997",

doi = "10.1515/MGMC.1997.20.5.293",

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T1 - Synthesis of boron substituted stannacyclohexadienes by a competitive metathesis

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AU - Eisen, Moris S.

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N2 - The reaction of phenyl borondibromide (PhBBr2) with 1,1-n-dibutylstanna-2,5-cyclohexadiene (8) produces, along with the expected phenylbora-2,5-cyclohexadiene (1), a mixture of boron substituted stannacyclohexadiene compounds 2 and 3 in a ratio of 1:2 respectively. Compounds 2 and 3 are in equilibrium at room temperature. The initial formation of either 2 or 3 is presumably the result of a metathesis reaction of the PhBBr2 with the double allylic C-H bond of the starting 1,1-n-dibutylstanna-2,5-cyclohexadiene (8), yielding compound 2, or with the allylic C-H bond of the 1,3-hydrogen isomerized starting stannacycle 8 (1,1-n-dibutylstanna-2,4-cyclohexadiene), yielding compound 3. The pseudo-first order rate of conversion from 2 ⇒ 3 was measured by an NMR spin population transfer technique to be k1 = 7.18 s-1 (2, 0.034M; T1 =1.6 s) while k-1 = was found to be 3.29 s-1 (T1 = 1.5 s), yielding an equilibrium constant of 2.18 at 298 K. The coalescence rate constant was calculated to be 235 s-1 which was not reached by heating the sample up to 383 K.

AB - The reaction of phenyl borondibromide (PhBBr2) with 1,1-n-dibutylstanna-2,5-cyclohexadiene (8) produces, along with the expected phenylbora-2,5-cyclohexadiene (1), a mixture of boron substituted stannacyclohexadiene compounds 2 and 3 in a ratio of 1:2 respectively. Compounds 2 and 3 are in equilibrium at room temperature. The initial formation of either 2 or 3 is presumably the result of a metathesis reaction of the PhBBr2 with the double allylic C-H bond of the starting 1,1-n-dibutylstanna-2,5-cyclohexadiene (8), yielding compound 2, or with the allylic C-H bond of the 1,3-hydrogen isomerized starting stannacycle 8 (1,1-n-dibutylstanna-2,4-cyclohexadiene), yielding compound 3. The pseudo-first order rate of conversion from 2 ⇒ 3 was measured by an NMR spin population transfer technique to be k1 = 7.18 s-1 (2, 0.034M; T1 =1.6 s) while k-1 = was found to be 3.29 s-1 (T1 = 1.5 s), yielding an equilibrium constant of 2.18 at 298 K. The coalescence rate constant was calculated to be 235 s-1 which was not reached by heating the sample up to 383 K.

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DO - 10.1515/MGMC.1997.20.5.293

M3 - 文章

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JO - Main Group Metal Chemistry

JF - Main Group Metal Chemistry

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Synthesis of boron substituted stannacyclohexadienes by a competitive metathesis

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