Aryltrimethylgermane cation radicals were generated by nanosecond transient absorption spectroscopy. Transient kinetics experiments show that the aryltrimethylgermane cation radicals react with added nucleophiles in reactions that are first-order in both the cation radicals and the nucleophiles. Preparative photo-oxidation experiments demonstrate that the intermediate cation radicals react with nucleophiles, resulting in aryl-Ge or Me-Ge nucleophile-assisted fragmentations. The aryltrimethylgermane cation radicals were found to react more slowly than analogous stannane cation radicals; however, loss of the thermodynamically disfavored aryl radicals remains competitive with methyl radical loss.
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