“Aurophilicity” as a Consequence of Relativistic Effects: The Hexakis(triphenylphosphaneaurio)methane Dication [(Ph 3 PAu) 6 C] 2⊕

The class of “porcupine compounds” , includes the title cation 1 , whose structure has been determined as the BPh 4 salt. The analytically, mass‐spectrometrically and crystallographically detected interstitial C atom occupies the crystallographic inversion center in an octahedron composed of gold atoms: the structure is probably stabilized by AuċAu interactions. The periphery of tetraauriomethanes is apparently “aurophile” with respect to further LAu ⊕ ions, so that the hypervalent complex cation [C(AuL) 6 ] 2⊕ is formed spontaneously. The supposedly un centered octahedral cluster cations formulated previously as (AuL)   6 2⊕were in fact probably indentical with the C‐centered species described here.