A Unique Synthetic Route toward a 1,2‐Dihydrodigermene <i>via</i> Formal <i>α</i>‐Elimination of Bromo and Silyl Groups from a Bromo(phenylsilyl)germane

Abstract A 1,2‐dihydrodigermene bearing Tbb {4‐ t ‐butyl‐1,3‐bis[bis(trimethylsilyl)methyl]phenyl} groups was successfully synthesized and isolated via formal α ‐elimination of bromo and silyl groups from the corresponding Tbb‐substituted boromo(phenylsilyl)germane. This novel synthetic method is conducted under mild conditions, representing a significant advantage in the field concerned. The synthesized 1,2‐dihydrodigermene was characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray crystallography. In the 1 H NMR spectrum, the Ge− H unit was found to be less electronically affected from the substituents compared to that of the previously reported 1,2‐dihydrodigermene. Moreover, the UV/vis spectra at various temperatures indicated the formation of the isomeric (dihydrogermyl)germylene. In fact, the 1,2‐dihydrodigermene once isolated reacted with DMAP in solution to afford the corresponding complex of the (dihydrogermyl)germylene.