Effects of Geminal Methyl Groups on the Tunnelling Rates in the Ring Opening of Cyclopropylcarbinyl Radical at Cryogenic Temperature

Description:

Article on the effects of geminal methyl groups on the tunnelling rates in the ring opening of cyclopropylcarbinyl radical at cryogenic temperature.

Creator(s):
Creation Date: 2011  
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
Usage:
Total Uses: 335
Past 30 days: 24
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Creator (Author):
Zhang, Xue

University of North Texas

Creator (Author):
Hrovat, David A.

University of North Texas

Creator (Author):
Datta, Ayan

University of North Texas

Creator (Author):
Borden, Weston T., 1943-

University of North Texas

Publisher Info:
Place of Publication: [Cambridge, England]
Date(s):
  • Creation: 2011
Description:

Article on the effects of geminal methyl groups on the tunnelling rates in the ring opening of cyclopropylcarbinyl radical at cryogenic temperature.

Degree:
Department: Chemistry
Note:

Zhang, X., Hrovat, D.A., Datta, A., Borden, W.T. (2011) Effects of geminal methyl groups on the tunneling rates in the ring opening of cyclopropylcarbinyl radical at cryogenic temperatures, Org. Biomol. Chem. (communication), 9, DOI: 10.1039/C0OB01238F - Reproduced by permission of The Royal Society of Chemistry.

Note:

Abstract: CVT + SCT calculations on the rate of tunnelling at 20 K in the ring opening of cyclopropylcarbinyl radical, substituted with geminal methyl groups at a ring carbon (1b), have been performed. The calculations predict that, contrary to expectations based on the effect of mass on the rate of tunnelling, the geminal methyl substituents in 1b should make the rate of ring opening to 1,1-dimethyl-3-butenyl radical (2b) 10(4) times faster than the rate of ring opening of unsubstituted cyclopropylcarbinyl radical (1a) to 3-butenyl radical (2a) and almost 10(6) times faster than the rate of ring opening of 1b to 2,2-dimethyl1-3-butenyl radical (2c). The reasons for these unexpected findings are discussed.

Physical Description:

4 p.

Language(s):
Subject(s):
Keyword(s): tunnelling | geminal methyl groups | cyclopropylcarbinyl radicals
Source: Organic and Biomolecular Chemistry, 2011, Cambridge: Royal Society of Chemistry (Great Britain), pp.3142-3145
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1039/C0OB01238F
  • ARK: ark:/67531/metadc71802
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Organic and Biomolecular Chemistry
Issue: 9
Page Start: 3142
Page End: 3145
Pages: 4
Peer Reviewed: Yes