Synthesis of the gold analogue of the elusive doubly protonated water molecule

Hubert Schmidbaur, Stefan Hofreiter, Martin Paul

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109 Scopus citations

Abstract

SINGLY coordinated metal cations of the type (L)M+ (where M is Cu, Ag or Au, and L is a donor ligand) are, in terms of their valence orbital characteristics, analogous to the proton1. The analogy is particularly pronounced for the gold cation, in which relativistic effects strongly contract the 6s valence orbital2, thereby permitting the incorporation of these proton analogues into stable molecular and ionic species having very short intramolecular bonds. Structural and stoichiometric parallels between gold cations and protons are illustrated by the species CH4 and C(AuL)4, NH4+ and N(AuL)4+ and OH3+ and O(AuL)3+ (refs 3-5), as well as by pairs of hypercoordinated cations such as CH5+ and C(AuL)5+ (refs 6, 7). We have recently synthesized the stable dicationic gold species [(LAu)6C]2+ and [(LAu)5N]2+ (refs 8, 9); their hydrogen counterparts, CH62+ and NH52+, have never been observed and are expected to be intrinsically unstable10. Here we describe the preparation of the first stable four-coordinated dicationic oxygen compound, [(LAu)4O]2+, whose analogue, the doubly protonated water molecule [H4O]2+, has been predicted to be stable only in the gas phase, or to appear as a transient state during proton transfer in super acid media11,12.

Original languageEnglish
Pages (from-to)503-504
Number of pages2
JournalNature
Volume377
Issue number6549
DOIs
StatePublished - 12 Oct 1995
Externally publishedYes

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