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

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 pi symmetry located on the Group 14 center.

Automated summary

An isostructural series of heavy Group 14 E(I) radical anions (Ge, Sn, Pb), stabilized by a bulky xanthene-based diamido ligand, were synthesized and characterized. The E(II) precursor complexes were one-electron reduced with sodium naphthalenide in THF, yielding the charge-separated radical anions as sodium salts. The comprehensive characterization using EPR spectroscopy, X-ray crystallography, and DFT analysis revealed that the spin density of the unpaired electron is mainly located in a p-orbital of pi symmetry on the Group 14 center in all cases.