Formation of selenaphosphole isomers from 1,2,4-selenadiphosphole by cycloaddition reaction. A synthetic and ab initio quantum chemical study

Sven Asmus, L. Nyulászi, Manfred Regitz

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Abstract

The reaction of 1,2,4-selenadiphosphole with dimethyl acetylenedicarboxylate resulted in a mixture of 1,2-selenaphosphole and 1,3-selenaphosphole at 110°C in boiling toluene. The mechanism has been interpreted by quantum chemical calculations. A cycloreversion process of the 1,2,4-selenadiphosphole has been ruled out on the basis of the high energy of the selenaphosphirene intermediate. A [4 + 2] cycloaddition of the acetylene on the selenadiphosphole results in the 1,2-selenaphosphole via an intermediate. A [3 + 2] cycloaddition via a single transition structure results in the 1,3-selenaphosphole. While the energies of the products differ considerably, transition structures on the two cycloaddition routes are predicted to have similar energies, explaining the observed 1:1 product ratio.

Original languageEnglish
Pages (from-to)1968-1972
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number10
Publication statusPublished - 2001

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Cycloaddition
Isomers
Acetylene
Toluene
Boiling liquids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "The reaction of 1,2,4-selenadiphosphole with dimethyl acetylenedicarboxylate resulted in a mixture of 1,2-selenaphosphole and 1,3-selenaphosphole at 110°C in boiling toluene. The mechanism has been interpreted by quantum chemical calculations. A cycloreversion process of the 1,2,4-selenadiphosphole has been ruled out on the basis of the high energy of the selenaphosphirene intermediate. A [4 + 2] cycloaddition of the acetylene on the selenadiphosphole results in the 1,2-selenaphosphole via an intermediate. A [3 + 2] cycloaddition via a single transition structure results in the 1,3-selenaphosphole. While the energies of the products differ considerably, transition structures on the two cycloaddition routes are predicted to have similar energies, explaining the observed 1:1 product ratio.",
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T1 - Formation of selenaphosphole isomers from 1,2,4-selenadiphosphole by cycloaddition reaction. A synthetic and ab initio quantum chemical study

AU - Asmus, Sven

AU - Nyulászi, L.

AU - Regitz, Manfred

PY - 2001

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N2 - The reaction of 1,2,4-selenadiphosphole with dimethyl acetylenedicarboxylate resulted in a mixture of 1,2-selenaphosphole and 1,3-selenaphosphole at 110°C in boiling toluene. The mechanism has been interpreted by quantum chemical calculations. A cycloreversion process of the 1,2,4-selenadiphosphole has been ruled out on the basis of the high energy of the selenaphosphirene intermediate. A [4 + 2] cycloaddition of the acetylene on the selenadiphosphole results in the 1,2-selenaphosphole via an intermediate. A [3 + 2] cycloaddition via a single transition structure results in the 1,3-selenaphosphole. While the energies of the products differ considerably, transition structures on the two cycloaddition routes are predicted to have similar energies, explaining the observed 1:1 product ratio.

AB - The reaction of 1,2,4-selenadiphosphole with dimethyl acetylenedicarboxylate resulted in a mixture of 1,2-selenaphosphole and 1,3-selenaphosphole at 110°C in boiling toluene. The mechanism has been interpreted by quantum chemical calculations. A cycloreversion process of the 1,2,4-selenadiphosphole has been ruled out on the basis of the high energy of the selenaphosphirene intermediate. A [4 + 2] cycloaddition of the acetylene on the selenadiphosphole results in the 1,2-selenaphosphole via an intermediate. A [3 + 2] cycloaddition via a single transition structure results in the 1,3-selenaphosphole. While the energies of the products differ considerably, transition structures on the two cycloaddition routes are predicted to have similar energies, explaining the observed 1:1 product ratio.

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