A Cationic Magnesium-Based Dithiolene Radical

Magnesium-based dithiolene radical
adduct (6•), the first
Group 2 element based dithiolene
radical, was synthesized via Ph3C+[B­(C6F5)4]−-mediated one-electron
oxidation of the THF-solvated neutral magnesium dithiolene complex
(5). Single-crystal X-ray diffraction analysis reveals
that 6• exists as a magnesium-based
dithiolene radical cation/[B­(C6F5)4]− anion pair. While electron paramagnetic resonance
(EPR) and computations indicate the predominantly dithiolene ligand-based
radical character of 6•, the weak satellite feature of the EPR spectrum of 6• originates from an admixture of
the 25Mg isotope (I = 5/2) with a natural
abundance of ca. 10%. The redox properties of 6• were explored using cyclic voltammetry.