title: New generation of organosilyl radicals by photochemically induced homolytic cleavage of silicon-boron bonds
abstract: Unlike bis(diethylamino)organosilylboranes, bis(diisopropylamino)organosilylboranes, which have UV absorption at longer wavelength than 300 nm, undergo photolysis to afford pairs of an organosilyl radical and a bis(diisopropylamino)boryl radical by homolytic scission of the silicon-boron bonds. Generation of organosilyl radical and organoboryl radical was confirmed by trapping experiments using TEMPO (2,2,6,6-tetramethylpiperidine N-oxyl). The organosilyl radical thus generated induces not only silylation of mono-olefins and silylative cyclization of dienes but also polymerization to afford polymers bearing organosilyl termini. On the other hand, the bis(diisopropylamino)boryl radical generated is not incorporated into the olefin adducts.
authors.affiliation: Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 606-8501, Japan.
authors.initials: A
authors.lastname: Matsumoto
authors.initials: Y
authors.lastname: Ito