A comparison of orbital interactions in the additions of phosphonyl and acyl radicals to double bonds

Elizabeth H. Krenske; Carl H. Schiesser

doi:10.1039/b714597g

A comparison of orbital interactions in the additions of phosphonyl and acyl radicals to double bonds

Elizabeth H. Krenske, Carl H. Schiesser

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9 Citations (Scopus)

Abstract

Calculation of the barriers for addition of the H₂P(=O)̇ and HC(=O)̇ radicals to alkenes, at the CCSD(T)/aug-cc-pVDZ//BHandHLYP/6- 311G** level, indicates that both radicals display ambiphilic behaviour. For the HC(=O)̇ radical this behaviour occurs because a secondary orbital interaction of the type π*_COHOMO acts in conjunction with the primary SOMOHOMO interaction to balance the SOMO→LUMO interaction. For the H₂P(O)̇ radical, on the other hand, the much higher-lying LUMO (the σ*_P-O orbital) allows for only minimal secondary interaction, and this radical's ambiphilic behaviour is therefore reflective of a balance between SOMO→LUMO and SOMO → HOMO interactions.

Original language	English
Pages (from-to)	854-859
Number of pages	6
Journal	Organic and Biomolecular Chemistry
Volume	6
Issue number	5
DOIs	https://doi.org/10.1039/b714597g
Publication status	Published - 2008

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title = "A comparison of orbital interactions in the additions of phosphonyl and acyl radicals to double bonds",

abstract = "Calculation of the barriers for addition of the H2P(=O{\.)} and HC(=O{\.)} radicals to alkenes, at the CCSD(T)/aug-cc-pVDZ//BHandHLYP/6- 311G** level, indicates that both radicals display ambiphilic behaviour. For the HC(=O{\.)} radical this behaviour occurs because a secondary orbital interaction of the type π*COHOMO acts in conjunction with the primary SOMOHOMO interaction to balance the SOMO→LUMO interaction. For the H2P(O{\.)} radical, on the other hand, the much higher-lying LUMO (the σ*P-O orbital) allows for only minimal secondary interaction, and this radical's ambiphilic behaviour is therefore reflective of a balance between SOMO→LUMO and SOMO → HOMO interactions.",

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AU - Krenske, Elizabeth H.

AU - Schiesser, Carl H.

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N2 - Calculation of the barriers for addition of the H2P(=O)̇ and HC(=O)̇ radicals to alkenes, at the CCSD(T)/aug-cc-pVDZ//BHandHLYP/6- 311G** level, indicates that both radicals display ambiphilic behaviour. For the HC(=O)̇ radical this behaviour occurs because a secondary orbital interaction of the type π*COHOMO acts in conjunction with the primary SOMOHOMO interaction to balance the SOMO→LUMO interaction. For the H2P(O)̇ radical, on the other hand, the much higher-lying LUMO (the σ*P-O orbital) allows for only minimal secondary interaction, and this radical's ambiphilic behaviour is therefore reflective of a balance between SOMO→LUMO and SOMO → HOMO interactions.

AB - Calculation of the barriers for addition of the H2P(=O)̇ and HC(=O)̇ radicals to alkenes, at the CCSD(T)/aug-cc-pVDZ//BHandHLYP/6- 311G** level, indicates that both radicals display ambiphilic behaviour. For the HC(=O)̇ radical this behaviour occurs because a secondary orbital interaction of the type π*COHOMO acts in conjunction with the primary SOMOHOMO interaction to balance the SOMO→LUMO interaction. For the H2P(O)̇ radical, on the other hand, the much higher-lying LUMO (the σ*P-O orbital) allows for only minimal secondary interaction, and this radical's ambiphilic behaviour is therefore reflective of a balance between SOMO→LUMO and SOMO → HOMO interactions.

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A comparison of orbital interactions in the additions of phosphonyl and acyl radicals to double bonds

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