Cluster Fusion: Face‐Fused Nine‐Atom Deltahedral Clusters in [Sn 14 Ni(CO)] 4−

The title anion was synthesized by heating dimethylformamide (DMF) solution of the known Ni‐centered and Ni(CO)‐capped tin clusters [Ni@Sn 9 Ni(CO)] 3− . The new anion represents the first example of face‐fused nine‐atom molecular clusters. The two clusters are identical elongated tricapped trigonal prisms of nido ‐[Sn 8 Ni(CO)] 6− with nickel at one of the capping positions. They are fused along a triangular face adjacent to a trigonal prismatic base and made of two Sn and one Ni atoms. The new anion is structurally characterized by single‐crystal X‐ray diffraction in the compound (K[222‐crypt]) 4 [Sn 14 Ni(CO)]⋅DMF. Its presence in solution is corroborated by electrospray mass spectrometry.