ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, The University of Melbourne, Victoria, 3010, Australia.
Chem Commun (Camb). 2012 Aug 28;48(67):8326-8. doi: 10.1039/c2cc33856d. Epub 2012 Jul 13.
High level calculations suggest that homolytic substitution (S(H)2) by alkyl radicals at sulfur proceeds through a mechanism that is assisted and dominated by LP → SOMO interactions; in the absence of these interactions, S(H)2 chemistry at sulfur is predicted to be virtually impossible. G3(MP2)-RAD calculations suggest that cyclization of the tert-butylsulfonylbutyl radical 2 (n = 2) proceeds with a rate constant of 1.7 × 10(-24) s(-1) at 80°, some 28 orders of magnitude slower than its sulfide cousin (n = 0).
高水平计算表明，硫原子上的自由基的均裂取代（S(H)2）通过 LP→SOMO 相互作用辅助和主导的机制进行；在没有这些相互作用的情况下，预计硫原子上的 S(H)2 化学几乎是不可能的。G3(MP2)-RAD 计算表明，叔丁基磺酰基丁基自由基 2（n = 2）的环化反应在 80°C 下的速率常数为 1.7×10(-24) s(-1)，比其硫代物（n = 0）慢约 28 个数量级。
