An unprecedented process involving normal and redox transmetallation reactions between Hg and Pt affording the unexpected K[Pt2[CH2C(O)Me]6(mu-Cl)3] complex: the key role of X-ray powder diffraction in unravelling its nature and structure.

[Hg{CH2C(O)Me}2] reacts with K[PtCl3(CH2=CH2)](2 : 1 molar ratio) to give K[Pt2{CH2C(O)Me}6(mu-Cl)3] (1); the intermediate [Pt{CH2C(O)Me}Cl2(CH2=CH2)]- has been detected in solution and isolated as a Me4N+ salt; the process occurs through successive normal and redox transmetallation reactions and an ab initio X-ray powder diffraction study of has proven to be essential to establish its nature.