Homoleptic Trifluoromethyl Derivatives of AgI and AgIII

The homoleptic silver(I) compound [PPh4][CF3AgCF3] (1) provides a convenient entry to the homoleptic silver(III) derivative [PPh4][Ag(CF3)4] (2). Once isolated as pure substances, these compounds exhibit marked thermal stabilities. Their structural and spectroscopic properties have been experimentally established. Moreover, their electronic structures have been calculated by theoretical methods. The electronic structure of the oxidized species [Ag(CF3)4]− provides a new case of ligand‐field inversion caused by the CF3 ligands. Upside down! The homoleptic organosilver(III) compound [Ag(CF3)4]− has near perfect square planar geometry in the simple [PPh4][Ag(CF3)4] salt. The unconventional CF3 groups induce ligand‐field inversion in its electronic structure, as calculated by theoretical methods.