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

Abstract: Group 13 M-I compounds often disproportionate into M-0 and M-III. Here, however, we show that the reaction of the M-I salt of the weakly coordinating alkoxyaluminate [Ga-I(C6H5F)(2)](+)[Al(ORF)(4)](-) (R-F = C(CF3)(3)) with 2,2'-bipyridine (bipy) yields the paramagnetic and distorted octahedral [Ga(bipy)(3)](2+center dot){[Al(ORF)(4)](-)}(2) complex salt. While the latter appears to be a Ga-II compound, both, EPR and DFT investigations assign a ligand-centred [Ga-III{(bipy)(3)}(center dot)](2+) radical dication. Surprisingly, the application of the heavier homologue [(I)n(I)(C6H5F)(2)](+)[Al(ORF)(4)](-) leads to aggregation and formation of the homonuclear cationic triangular and rhombic [In-3(bipy)(6)](3+), [In-3(bipy)(5)](3+) and [In-4(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 [M-3](3+){[Al(ORF)(4)](-)}(3) and [M-4](4+){[Al(ORF)(4)](-)}(4) salts

Object Details

• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch
• Notes: Nature Communications. 6 (2015), article no. 8288, DOI 10.1038/ncomms9288, issn: 2041-1723 ; IN COPYRIGHT http://rightsstatements.org/page/InC/1.0 rs

Classification and Topics

• Classification: Chemie
• Keyword: Ligand ; Anion

Contributors, Places and Time

• Event: Veröffentlichung
• (where): Freiburg
• (who): Universität
• (when): 2015
• Creator: Lichtenthaler, Martin R. ; Stahl, Florian ; Kratzert, Daniel ; Heidinger, Lorenz ; Hamann, Julian ; Himmel, Daniel ; Weber, Stefan ; Krossing, Ingo
• Contributor: Albert-Ludwigs-Universität Freiburg. Fakultät für Chemie und Pharmazie ; Institut für Anorganische und Analytische Chemie. Freiburg im Breisgau ; Albert-Ludwigs-Universität Freiburg

Further information

• DOI: 10.1038/ncomms9288
• URN: urn:nbn:de:bsz:25-freidok-133068
• Rights: Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Last update: 25.03.2025, 1:53 PM CET