Crystalline Germanium(I) and Tin(I) Centered Radical Anions.

Abstract

An isostructural series of heavy Group 14 E(I) radical anions (Ge, Sn, Pb), stabilized by a bulky xanthene‐based diamido ligand are reported. The radical anions were synthesised by the one‐electron reduction of their corresponding E(II) precursor complexes with sodium naphthalenide in THF, yielding the radical anions as charge‐separated sodium salts. The series of main group radicals have been comprehensively characterized by EPR spectroscopy, X‐ray crystallography and DFT analysis, which reveal that in all cases, the spin density of the unpaired electron almost exclusively resides in a p‐orbital of π symmetry located on the Group 14 center.