期刊
ORGANIC & BIOMOLECULAR CHEMISTRY
卷 13, 期 8, 页码 2310-2316出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4ob02434f
关键词
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资金
- Australian Research Council through the Centres of Excellence Scheme
- Australian Government
- Australian Research Council
- ARC Future Fellowship
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 degrees C rate constants (k(c)) that lie between 10(4)-10(7) s(-1) were determined experimentally and correlate with expectations based on leaving group ability. Activation energies (E-act) 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.
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