Alkyl-GeMe 3 : Neutral Metalloid Radical Precursors upon Visible-Light Photocatalysis.

Single-electron transfer (SET) oxidation of ionic hypervalent complexes, in particular alkyltrifluoroborates (Alkyl-BF 3 - ) and alkylbis(catecholato)silicates (Alkyl-Si(cat) 2 - ), have contributed substantially to alkyl radical generation compared to alkali or alkaline earth organometallics because of their excellent activity-stability balance. Herein, another proposal is reported by using neutral metalloid compounds, Alkyl-GeMe 3 , as radical precursors. Alkyl-GeMe 3 shows comparable activity to that of Alkyl-BF 3 - and Alkyl-Si(cat) 2 - in radical addition reactions. Moreover, Alkyl-GeMe 3 is the first successful group 14 tetraalkyl nucleophile in nickel-catalyzed cross-coupling. Meanwhile, the neutral nature of these organogermanes offset the limitation of ionic precursors in purification and derivatization. A preliminary mechanism study suggests that an alkyl radical is generated from a tetraalkylgermane radical cation with the assistance of a nucleophile, which may also result in the development of more non-ionic alkyl radical precursors with a metalloid center.