Absolute rates of intermolecular carbon-hydrogen abstraction reactions by fluorinated radicals
Shtarev, AB; Tian, F; Dolbier, WR; Smart, BE
| HERO ID | 4854588 |
|---|---|
| In Press | No |
| Year | 1999 |
| Title | Absolute rates of intermolecular carbon-hydrogen abstraction reactions by fluorinated radicals |
| Authors | Shtarev, AB; Tian, F; Dolbier, WR; Smart, BE |
| Journal | Journal of the American Chemical Society |
| Volume | 121 |
| Issue | 32 |
| Page Numbers | 7335-7341 |
| Abstract | Using competition kinetic methodology, absolute rate constants for bimolecular hydrogen abstraction from a variety of organic substrates in solution have been obtained for the n-C4H9CF2CF2., n-C4F9., and i-C3F7. radicals. Fluorine substitution substantially increases the reactivity of alkyl radicals with respect to C-H abstraction, with the secondary radical being most reactive. A wide range of substrate reactivities (5200-fold) was observed, with the results being discussed in terms of an interplay of thermodynamic, polar, steric, stereoelectronic, and electrostatic/field effects on the various C-H abstraction transition states. Representative carbon-hydrogen bond dissociation energies of a number of ethers and alcohols have been calculated using DFT methodology. |
| Doi | 10.1021/ja990521q |
| Wosid | WOS:000082250000008 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |