A trialkylborohydide-initiated hydrogermylation of aromatic alkenes is reported along with a DFT-supported mechanism following the course of a ‘living’ process.

Sodium trialkylborohydrides were found to be selective catalysts for the hydrogermylation of aromatic alkenes. Addition of phenylgermane and diphenylgermane in the presence of 10 mol% of NaHB(sec-Bu)3 proceeded in a highly selective manner to give – in contrast to the analogous hydrosilylation process – β-germylated products. The nature of this process was explained with the aid of DFT calculations and it was proposed that the mechanism proceeds via a trisubstituted germanide anion whose attack on the terminal vinyl carbon is the source of selectivity.