Strukturen, Bindungsanalyse und Reaktivität eines dikationischen Digallens und eines Diindens, die trans‐gefaltete Ditetrylene nachahmen

Abstract

The reaction of bisdicyclohexylphosphinoethane (dcpe) and the subvalent MI sources [MI(PhF)2][pf] (M = Ga+, In+; [pf]− = [Al(ORF)4]−; RF = C(CF3)3) yielded the salts [{M(dcpe)}2][pf]2, containing the first dicationic, trans‐bent digallene and diindene structures reported so far. The non‐classical MI⇆MI 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 analyses (Energy Decomposition Analysis with the combination of Natural Orbitals for Chemical Valence)and is compared to that in the isoelectronic, but neutral digermenes and distannenes. The dissolved [{Ga(dcpe)}2]2+([pf]−)2 readily reacts with 1‐hexene, cyclooctyne, diphenyldisulfide, diphenylphosphine and under mild conditions at rt. This reactivity is analyzed and rationalized.