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

Nature communications, 2015

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(OR(F))4](-) (R(F)=C(CF3)3) with 2,2'-bipyridine (bipy) yields the paramagnetic and distorted octahedral [Ga(bipy)3](2+)(•){[Al(OR(F))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}(•)](2+) radical dication. Surprisingly, the application of the heavier homologue [(I)n(I)(C6H5F)2](+)[Al(OR(F))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 furthe...

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