Reaction of [AuCl(terpy-κ-N)]Cl with an excess of sodium azide did not result in the expected exchange of the chlorido by an azido ligand to give [Au(N)(terpy-κ-N)]. Instead, X-ray structure analysis showed that the isolated product is [Au(N)(terpy-κ-N)], in which the terpyridine ligand is in a very rare monodentate coordination mode. This is also the dominant species in solution, together with a minor amount of [Au(N)(terpy-κ-N)]. The stability of the tris(azido)gold(iii) moiety relative to other possible species was also confirmed by DFT calculations.
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