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

Krenske, Elizabeth H. and Schiesser, Carl H. (2008) A comparison of orbital interactions in the additions of phosphonyl and acyl radicals to double bonds. Organic & Biomolecular Chemistry, 6 5: 854-859. doi:10.1039/b714597g


Author Krenske, Elizabeth H.
Schiesser, Carl H.
Title A comparison of orbital interactions in the additions of phosphonyl and acyl radicals to double bonds
Journal name Organic & Biomolecular Chemistry   Check publisher's open access policy
ISSN 1477-0520
1477-0539
Publication date 2008-01
Sub-type Article (original research)
DOI 10.1039/b714597g
Open Access Status Not Open Access
Volume 6
Issue 5
Start page 854
End page 859
Total pages 6
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Formatted abstract
Calculation of the barriers for addition of the H2P([double bond, length as m-dash]O)˙ and HC([double bond, length as m-dash]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([double bond, length as m-dash]O)˙ radical this behaviour occurs because a secondary orbital interaction of the type π*C[double bond, length as m-dash]O←HOMO acts in conjunction with the primary SOMO←HOMO interaction to balance the SOMO→LUMO interaction. For the H2P([double bond, length as m-dash]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.
Keyword Electrophiles
Cyclization
Reactivity
Azaenynes
Olefins
Lactams
Imines
Silyl
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Chemistry and Molecular Biosciences
 
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