Reactions of the tert-Butylthiyl Radical with Organometallic Compounds and Alkenes

Article abstract of DOI:10.1021/ja00201a044

Absolute rate constants for the reactions of the tert-butylthiyl radical with a variety of substrates were measured by using a combination of laser flash photolysis techniques and product studies.Reactions with organometallic substrates such as boranes, phosphines, and phosphites were extremely rapid with rate constants in the range 1E8 - 1E9 M^-1 s^-1.By contrast, addition to a simple olefin, oct-1-ene, was ca. 100 times less rapid.However, 1,1-diphenyl- and 1,1-dicyclopropylethylene were remarkably efficient traps for tert-butylthiyl and scavenged the radicalwith rate constants of 9.9*1E8 and 2.4*1E8 M^-1 s^-1, respectively.