Mechanism and Unusual Fragmentation Selectivities of Aryltrialkylstannane Cation Radicals

Aryltrialkylstannane cation radicals were generated and characterized by nanosecond transient absorption spectroscopy. Kinetics show the fragmentations of the stannane cation radicals occur by a bimolecular, nucleophile-assisted mechanism (SN2). Consistent with this hypothesis, steric effects on both the nucleophile and the stannane cation radicals were observed. Steady-state, preparative photooxidation experiments show that...