Aurophilicity as Concerted Effect: Relativistic MO Calculations on Carbon‐Centered Gold Clusters

Three features must be taken into consideration in discussing the bonding in carbon‐centered gold clusters: the tangential AuAu bonds, the radial bonds between Au and the central atom as well as between Au and the outer ligands, and the preference for 6s‐5d over 6s‐6p hybridization. Nonrelativistic and relativistic MO calculations revealed that the formally closed d¹⁰ shell of the Au^⊕ ions in the cluster [(LAu)₆C]^2⊕ is increasingly disrupted by interaction with the other Au centers, the central atom, and the ligands L, thereby increasing the probability of AuAu interactions.