A crystalline T-shaped planar group 14 anion.

Isolable T-shaped planar pnictogen compounds R 3 Pn were reported more than three decades ago and have been attracting burgeoning interest in recent years; T-shaped planar group 14 anions, isoelectronic to R 3 Pn, however, are still unknown. Herein, we report the synthesis, full characterization, and reactivity of the first crystalline T-shaped planar group 14 anion 4 bearing a trinitrogen pincer ligand. DFT calculations indicate that the tricoordinate germanium center features both an unoccupied 4p orbital and two lone pairs of electrons. Its electron-rich nature allows for the nucleophilic attack on the methyl iodine giving methyl-substituted complex 5 and facile oxidation of the germanium center by elemental sulfur and selenium to furnish unpresented organic anions bearing terminal Ge[double bond, length as m-dash]Ch (Ch = S or Se) double bonds.