Abstract
RECENT work1–5 has shown that gold-based ligands in compounds of carbon and nitrogen can induce novel molecular structures with coordination numbers at C and N as high as 5 and 6. These phenomena must be ascribed to metal–metal interactions (Au…Au), which can overrule bonding in classical configurations. Here we describe a study of the molecular structures of tetra(auro)ammonium ((LAu)4N+) and tetra(auro)arsonium ((LAu)4As+) cations (where L is a ligand). We find that the classical tetrahedral structure in these four-coordinate compounds is abandoned in favour of a square-pyramidal geometry once the radius of the central element is too large to allow for metal–metal bonding in a tetrahedral geometry. Thus, whereas the nitrogen compounds adopt a tetrahedral structure, for the larger arsenic atom an arsenic-capped square of gold atoms represents a more favourable core geometry. We have not yet been able to prepare the intermediate phosphorus compound, but we expect it also to have the square-pyramidal structure.
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Zeller, E., Beruda, H., Kolb, A. et al. Change of coordination from tetrahedral gold–ammonium to square-pyramidal gold–arsonium cations. Nature 352, 141–143 (1991). https://doi.org/10.1038/352141a0
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DOI: https://doi.org/10.1038/352141a0
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