Structures, Bonding Analyses and Reactivity of a Dicationic Digallene and Diindene Mimicking trans-bent Ditetrylenes.

The reaction of bisdicyclohexylphosphinoethane (dcpe) and the subvalent M sources [M (PhF) ][pf] (M=Ga , In ; [pf] =[Al(OR ) ] ; R =C(CF ) ) yielded the salts [{M(dcpe)} ][pf] , containing the first dicationic, trans-bent digallene and diindene structures reported so far. The non-classical M ⇆M double bonds are surprisingly short and display a ditetrylene-like structure. The bonding situation was extensively analyzed by quantum chemical calculations, QTAIM (Quantum Theory of Atoms in Molecules) and EDA-NOCV (Energy Decomposition Analysis with the combination of Natural Orbitals for Chemical Valence) analyses and is compared to that in the isoelectronic and isostructural, but neutral digermenes and distannenes. The dissolved [{Ga(dcpe)} ] ([pf] ) readily reacts with 1-hexene, cyclooctyne, diphenyldisulfide, diphenylphosphine and under mild conditions at room temperature. This reactivity is analyzed and rationalized.