Cluster Fusion: Face-Fused Nine-Atom Deltahedral Clusters in [Sn14Ni(CO)]4

The title anion was synthesized by heating dimethylformamide (DMF) solution of the known Ni‐centered and Ni(CO)‐capped tin clusters [Ni@Sn9Ni(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‐[Sn8Ni(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[Sn14Ni(CO)]⋅DMF. Its presence in solution is corroborated by electrospray mass spectrometry. Face to face: Two nine‐atom clusters, each in the shape of a tricapped trigonal prism (the prismatic edges parallel to the threefold axes are shown as broken lines), are “welded” at a triangular face made of two Sn and one Ni atoms to form [Sn14Ni(CO)]4−. The “welding” is achieved by heating of an ethylenediamine solution of the known clusters [Ni@Sn9Ni(CO)]3−.