Cationic cluster formation versus disproportionation of low-valent indium and gallium complexes of 2,2’-bipyridine

Martin R. Lichtenthaler, Florian Stahl, Daniel Kratzert, Lorenz Heidinger, Erik Schleicher, Julian Hamann, Daniel Himmel, Stefan Weber and Ingo Krossing ()
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Martin R. Lichtenthaler: Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg
Florian Stahl: Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg
Daniel Kratzert: Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg
Lorenz Heidinger: Institut für Physikalische Chemie and Freiburg Institute of Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg
Erik Schleicher: Institut für Physikalische Chemie and Freiburg Institute of Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg
Julian Hamann: Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg
Daniel Himmel: Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg
Stefan Weber: Institut für Physikalische Chemie and Freiburg Institute of Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg
Ingo Krossing: Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg

Nature Communications, 2015, vol. 6, issue 1, 1-9

Abstract: Abstract Group 13 MI compounds often disproportionate into M0 and MIII. Here, however, we show that the reaction of the MI salt of the weakly coordinating alkoxyaluminate [GaI(C6H5F)2]+[Al(ORF)4]− (RF=C(CF3)3) with 2,2’-bipyridine (bipy) yields the paramagnetic and distorted octahedral [Ga(bipy)3]2+•{[Al(ORF)4]−}2 complex salt. While the latter appears to be a GaII compound, both, EPR and DFT investigations assign a ligand-centred [GaIII{(bipy)3}•]2+ radical dication. Surprisingly, the application of the heavier homologue [InI(C6H5F)2]+[Al(ORF)4]− leads to aggregation and formation of the homonuclear cationic triangular and rhombic [In3(bipy)6]3+, [In3(bipy)5]3+ and [In4(bipy)6]4+ metal atom clusters. Typically, such clusters are formed under strongly reductive conditions. Analysing the unexpected redox-neutral cationic cluster formation, DFT studies suggest a stepwise formation of the clusters, possibly via their triplet state and further investigations attribute the overall driving force of the reactions to the strong In−In bonds and the high lattice enthalpies of the resultant ligand stabilized [M3]3+{[Al(ORF)4]−}3 and [M4]4+{[Al(ORF)4]−}4 salts.

Date: 2015
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DOI: 10.1038/ncomms9288

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