Modes of Neighbouring Group Participation by the Methyl Selenyl Substituent in β-Methylselenylmethyl-substituted 1-Phenylethyl Carbenium Ions
Selenium substituents which are disposed β to an electron deficient centre, such as a carbocation p-orbital, or the π* orbital of an electron deficient p-system, interact in a stabilising way by a combination of C-Se hyperconjugation (σSe-C–π* interaction), and a through-space homoconjugative nSe–π*...
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MDPI AG
2013-09-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/18/10/11705 |
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doaj-d9bd6bf3ac004bc6bd4bb1ccb009c5202020-11-25T01:46:59ZengMDPI AGMolecules1420-30492013-09-011810117051171110.3390/molecules181011705Modes of Neighbouring Group Participation by the Methyl Selenyl Substituent in β-Methylselenylmethyl-substituted 1-Phenylethyl Carbenium IonsBenjamin L. HarrisJonathan M. WhiteSelenium substituents which are disposed β to an electron deficient centre, such as a carbocation p-orbital, or the π* orbital of an electron deficient p-system, interact in a stabilising way by a combination of C-Se hyperconjugation (σSe-C–π* interaction), and a through-space homoconjugative nSe–π* interaction. The relative importance of these two modes of interaction is dependant on the electron demand of the cation, with hyperconjugation predominating for low electron demand systems, and the nSe–π* interaction predominating for high electron demand cations.http://www.mdpi.com/1420-3049/18/10/11705hyperconjugationstereoelectronic effectsselenium interactions |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Benjamin L. Harris Jonathan M. White |
| spellingShingle |
Benjamin L. Harris Jonathan M. White Modes of Neighbouring Group Participation by the Methyl Selenyl Substituent in β-Methylselenylmethyl-substituted 1-Phenylethyl Carbenium Ions Molecules hyperconjugation stereoelectronic effects selenium interactions |
| author_facet |
Benjamin L. Harris Jonathan M. White |
| author_sort |
Benjamin L. Harris |
| title |
Modes of Neighbouring Group Participation by the Methyl Selenyl Substituent in β-Methylselenylmethyl-substituted 1-Phenylethyl Carbenium Ions |
| title_short |
Modes of Neighbouring Group Participation by the Methyl Selenyl Substituent in β-Methylselenylmethyl-substituted 1-Phenylethyl Carbenium Ions |
| title_full |
Modes of Neighbouring Group Participation by the Methyl Selenyl Substituent in β-Methylselenylmethyl-substituted 1-Phenylethyl Carbenium Ions |
| title_fullStr |
Modes of Neighbouring Group Participation by the Methyl Selenyl Substituent in β-Methylselenylmethyl-substituted 1-Phenylethyl Carbenium Ions |
| title_full_unstemmed |
Modes of Neighbouring Group Participation by the Methyl Selenyl Substituent in β-Methylselenylmethyl-substituted 1-Phenylethyl Carbenium Ions |
| title_sort |
modes of neighbouring group participation by the methyl selenyl substituent in β-methylselenylmethyl-substituted 1-phenylethyl carbenium ions |
| publisher |
MDPI AG |
| series |
Molecules |
| issn |
1420-3049 |
| publishDate |
2013-09-01 |
| description |
Selenium substituents which are disposed β to an electron deficient centre, such as a carbocation p-orbital, or the π* orbital of an electron deficient p-system, interact in a stabilising way by a combination of C-Se hyperconjugation (σSe-C–π* interaction), and a through-space homoconjugative nSe–π* interaction. The relative importance of these two modes of interaction is dependant on the electron demand of the cation, with hyperconjugation predominating for low electron demand systems, and the nSe–π* interaction predominating for high electron demand cations. |
| topic |
hyperconjugation stereoelectronic effects selenium interactions |
| url |
http://www.mdpi.com/1420-3049/18/10/11705 |
| work_keys_str_mv |
AT benjaminlharris modesofneighbouringgroupparticipationbythemethylselenylsubstituentinbmethylselenylmethylsubstituted1phenylethylcarbeniumions AT jonathanmwhite modesofneighbouringgroupparticipationbythemethylselenylsubstituentinbmethylselenylmethylsubstituted1phenylethylcarbeniumions |
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1725016877443317760 |