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A neutral octa‐nuclear AuI‐cluster (2) with molecular formula [(Cy‐cAACPAu)4(AuCl)4] [Cy‐cAAC=:C(N‐2,6‐iPr2C6H3)(C6H10)(CMe2)(CH2)] has been isolated, and structurally characterized by single‐crystal X‐ray diffraction. 2 has been further studied by NMR and ESI‐MS. The μ3‐P bridged AuI‐cluster 2 possesses a C2 axis that passes through the two Au atoms positioned oppositely of the central AuI4P4 core,...