Understanding (the lack of) homolytic substitution chemistry of sulfones

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 x 10(-24) s(-1) at 80 degrees, some 28 orders of magnitude slower than its sulfide cousin (n = 0).