Abstract
Competition kinetic studies augmented with laser-flash photolysis and high-level computational techniques [G3(MP2)-RAD], with [COSMO-RS, SMD] and without solvent correction, provide kinetic parameters for the ring closures of a series of 4-(alkylseleno)butyl radicals 1. At 22 °C rate constants (kc) that lie between 104-107 s-1 were determined experimentally and correlate with expectations based on leaving group ability. Activation energies (Eact) were determined to lie between 10.6 (R = Ph2CH) and 28.0 (R = n-Bu) kJ mol-1, while log(A/s-1) values were generally between 9 and 10 in benzene. Computationally determined rate constants were in good-to-excellent agreement with those determined experimentally, with the COSMO-RS solvation model providing values that more closely resemble those from experiment than SMD.
Original language | English |
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Pages (from-to) | 2310-2316 |
Number of pages | 7 |
Journal | Organic and Biomolecular Chemistry |
Volume | 13 |
Issue number | 8 |
DOIs | |
Publication status | Published - 2015 |
Externally published | Yes |
Bibliographical note
Publisher Copyright:© The Royal Society of Chemistry 2015.