Stable GaX2, InX2 and TlX2 radicals

Andrey V. Protchenko, Deepak Dange, Jeffrey R. Harmer, Christina Y. Tang, Andrew D. Schwarz, Michael J. Kelly, Nicholas Phillips, Remi Tirfoin, Krishna Hassomal Birjkumar, Cameron Jones, Nikolas Kaltsoyannis, Philip Mountford, Simon Aldridge

The chemistry of the Group 13 metals is dominated by the +1 and +3 oxidation states, and simple monomeric M(II) species are typically short-lived, highly reactive species. Here we report the first thermally robust monomeric MX2 radicals of gallium, indium and thallium. By making use of sterically demanding boryl substituents, compounds of the type M(II)(boryl)2 (M = Ga, In, Tl) can be synthesized. These decompose above 130 °C and are amenable to structural characterization in the solid state by X-ray crystallography. Electron paramagnetic resonance and computational studies reveal a dominant metal-centred character for all three radicals (>70% spin density at the metal). M(II) species have been invoked as key short-lived intermediates in well-known electron-transfer processes; consistently, the chemical behaviour of these novel isolated species reveals facile one-electron shuttling processes at the metal centre.