We thank the EPSRC and the ETH for funding and the EPSRC National Mass Spectrometry Service, Swansea, for spectra, and we thank Markus Reiher (ETH) for helpful discussions.
Electron Transfer to Benzenes by Photoactivated Neutral Organic Electron Donor Molecules†
Article first published online: 2 MAR 2012
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 51, Issue 15, pages 3673–3676, April 10, 2012
How to Cite
Cahard, E., Schoenebeck, F., Garnier, J., Cutulic, S. P. Y., Zhou, S. and Murphy, J. A. (2012), Electron Transfer to Benzenes by Photoactivated Neutral Organic Electron Donor Molecules . Angew. Chem. Int. Ed., 51: 3673–3676. doi: 10.1002/anie.201200084
- Issue published online: 4 APR 2012
- Article first published online: 2 MAR 2012
- Manuscript Received: 4 JAN 2012
- 5Whereas the addition of an electron to benzene in its ground state is an extremely challenging reaction, there are many reports of aliphatic amines or other electron-rich species acting as electron donors to an excited state of benzene (irradiation at 254 nm). Promotion of an electron from the benzene HOMO to the LUMO occurs, and the amine transfers an electron to fill the hole thereby created. See:
- 5aJ. Chem. Soc. Chem. Commun. 1971, 916–917;, , , , ,
- 15The radical cation of 1,2-diphenylcyclopropane has been widely studied and is known to undergo facile ring opening; starting from either the cis or the trans isomer, stereomutation of 1,2-diphenylcyclopropane has been shown in the presence of appropriate electron acceptors using photoelectron transfer. However, to our knowledge, the radical anion has not previously been probed.
- 16aIsomerization upon irradiation at 254 nm: J. Org. Chem. 1971, 36, 66–72;, ,
- 18Gaussian 09, Revision A.01, M. J. Frisch et al. (see the Supporting Information for the full reference).
- 19This level of theory was shown to be reliable for the cyclopropyl radical cations:
- 19cEur. J. Org. Chem. 2003, 1454–1462; For an application of B3LYP for radical anions, see: J. Am. Chem. Soc. 2007, 129, 3211–3217. For a discussion of the failure of DFT in the treatment of radical cations, see: J. Phys. Chem. A 1998, 102, 7872–7877., ,
- 21At UCCSD(T) level the energy difference is −0.05 kcal mol−1.