The gold(I) phosphinine complexes [AuCl(C 5 H 2 P-2,6-Me 2 -4-Ph)] and [AuCl(C 5 H 2 P-2,4,6-Ph 3 )] were prepared and structurally characterised by single-crystal X-ray diffraction studies. In the former case, individual molecules are aggregated in the crystal as crossed dimers with an Au···Au distance of 3.60Å, compatible with a weak aurophilic interaction. In the latter case, intermolecular Au···π interactions involving the phosphinine ring are observed with Au···C distances in the range from ca. 3.32 to 3.44Å, which make [AuCl(C 5 H 2 P-2,4,6-Ph 3 )] the first structurally characterised example of intermolecular Au···π interactions involving a heteroarene.
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