On the Synthesis and Structure of 'Naked' Ga(I) and In(I) Salts and the Surprising Stability of Simple Ga(I) and In(I) Salts in the Coordinating Solvents Ether and Acetonitrile.

ABSTRACT

In this work, we present the solid-state structures of solvent-free Ga[pf] and In[pf] salts ([pf]-=[Al(ORF)4]-; RF=C(CF3)3), which are very rare examples of salts with truly 'naked' metal cations. Both salts may serve as starting materials for subvalent gallium and indium chemistry with very weakly coordinating ligands providing the freedom of choice for solvents and ligands for the future. On the other hand, we report and rationalize the formation and isolation of [M(OEt2)2][pf] and [M(MeCN)2][pf] (M=Ga, In), underlining the surprising stability of these subvalent group 13 M+ ions against disproportionation. Unexpectedly, dicoordinate and carbene analogous [M(L)2]+ ions with the [pf]- counterion are stable in L=acetonitrile and diethyl ether at room temperature, opening up possible applications for example in organic synthesis and catalysis.