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

Autor: Barthélemy A; Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany., Scherer H; Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany., Daub M; Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany., Bugnet A; Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany., Krossing I; Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Nov 20; Vol. 62 (47), pp. e202311648. Date of Electronic Publication: 2023 Oct 17.
DOI: 10.1002/anie.202311648
Abstrakt: The reaction of bisdicyclohexylphosphinoethane (dcpe) and the subvalent M I sources [M I (PhF) 2 ][pf] (M=Ga + , In + ; [pf] - =[Al(OR F ) 4 ] - ; R F =C(CF 3 ) 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 M I ⇆M I 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.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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