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

Angew Chem Int Ed Engl. 2022 May 16;61(21):e202201248. doi: 10.1002/anie.202201248. Epub 2022 Mar 23.

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.

Keywords: EPR Spectroscopy; Group 14 Elements; Main Group Elements; Radical Ions.