Does H₃O⁺ Really Act as a Ligand in the Solid State?

Abstract

The evidence for the existence of metal complexes containing H₃O⁺ as a ligand in the solid state is examined. Each of the 68 examples in the Cambridge Structural Database in which H₃O⁺ is bound to a transition metal, lanthanoid, actinoid, or main group metal ion is detailed and critically appraised. It is concluded that none of the reported examples of complexes containing coordinated H₃O⁺ have been unequivocally characterized and that they result from either curation errors or misinterpretations of the crystallographic data. These conclusions are supported by computational techniques, which show that three purported H₃O⁺ complexes based on the 1,4,7,10,13,16,21,24-octa-azabicyclo(8.8.8)hexacosane azacryptand skeleton are better described as aqua complexes, with protonation occurring at the amine ligand.