ORGN 481 |
| Stephen F. Nelsen, Department of Chemistry, Department of Chemistry, University of Wisconsin, Madisn, 1101 University Ave., Madison, WI 53706-1396 |
| The simplest form of the Marcus cross rate equation , k12=(kii kjj Kij fij)½ , only applies to reactions with one neutral component. If true, when the formal oxidation potential (Eo') and intrinsic reactivity (kii) are known, the rate constant with all other couples for which Eo', and kii are known may be calculated. The assumptions made in deriving it are incorrect, but in collaboration with Jack Pladziewicz (UW?Eau Claire) we have shown that for a wide variety of couples it well enough that measurement of Eo' and k12 values allows determination of a consistent set of kii values for 164 reactions between 53 couples. Conclusions from our work include that dielectric continuum theory does not predict solvent reorganization energies well at all and that intermolecular electronic coupling for most couples is remarkably constant and small, but that these reactions do not fit expectation for "nonadiabatic" reactions. |
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Synthetic Organic Electrochemistry
9:00 AM-11:30 AM, Wednesday, September 10, 2003 Sheraton New York -- Royal Ballroom A, Oral
Division of Organic Chemistry |