ORGN 360 |
| Howard Haubenstock, Department of Chemistry, College of Staten Island, City University of New York, 2800 Victory Blvd., Staten Island, NY 10314 and Ronald Sauers, Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, NJ 08903. |
| The effect of vinylic stabilization of a carbocationic center on competitive bridging at the cationic center by adjacent halogens has been studied by DFT and ab initio methods. In particular, conformational structural and energetic parameters of 4-halo-1-buten-3-yl cationic systems were explored. A significant reduction of halogen bridging resulting from vinylic stabilization of the cationic center was observed, primarily by comparison with the analogous saturated 1-halo-2-butylcations. Furthermore, major differences in the importance of bridging was found between chlorine and bromine, as well as between unsymmetrical and symmetrical bridging in the halonium ions derived from cis- or trans-2-butene. The importance of fluorine bridging was investigated by similar methods and comparisons will be made with the other halogens. |
|
Physical Organic, Materials, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Tuesday, September 9, 2003 Hilton New York -- Americas Hall 1, Poster
Division of Organic Chemistry |