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. 2023 Nov 20;62(47):e202311648.
doi: 10.1002/anie.202311648. Epub 2023 Oct 17.

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

Antoine Barthélemy  1 , Harald Scherer  1 , Michael Daub  1 , Alexis Bugnet  1 , Ingo Krossing  1
Affiliations

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

Antoine Barthélemy et al. Angew Chem Int Ed Engl. .

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 (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)}2 ]2+ ([pf]- )2 readily reacts with 1-hexene, cyclooctyne, diphenyldisulfide, diphenylphosphine and under mild conditions at room temperature. This reactivity is analyzed and rationalized.

Keywords: Density Functional Calculations; Main Group Elements; Non-Classical Double Bonds; Oxidative Addition Reactions; Weakly Coordinating Anion (WCA).

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