| Abstract | Tris(organothiyl)methyl radicals, RnMSC(SR )2, have been generated by the addition of a variety of transient RnM-radicals to the thione sulfur of three trithiocarbonates (dimethyl trithiocarbonate (2), 1,3-dithiolane-2-thione (3), and 1,3-dithiole-2-thione (4)) and their EPR parameters have been measured. All adducts to 3 and 4 adopt a conformation in which the RnM group and the semioccupied orbital at Cα are eclipsed, but the adducts to 2 adopt noneclipsed conformations. This behavior is attributed to differences in the extent of conjugative electron delocalization to the p-type lone pair of the sulfur which bears the RnM group. Tetrathiafulvalene (6) is formed by reaction of R3Sn· radicals with 4 (cf. ref 17). Its yield passes through a maximum because the R3Sn· can attack 6 at sulfur via an SH2 process. This produces acetylene and persistent 1-thiaallyl radicals, R3SnSC̄(S̄.)C̄(SCH)2, which exist in equilibrium with their diamagnetic dimers at ambient temperatures. © 1978 American Chemical Society. |
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