Exceeding Metal Capacity in Sandwich Complexes: Ligand‐Unsupported Docking of Extra Metal Moieties at Edges of a Metal Sheet Sandwich Complex

• Published in: Angewandte Chemie 2019-10, Vol.131 (43), p.15462-15467
• Main Authors: Ishikawa, Tomoko, Kawamura, Akino, Sugawa, Tsuyoshi, Moridaira, Risako, Yamamoto, Koji, Murahashi, Tetsuro
• Format: Article
• Language: English
• Subjects: Chemistry; Coordination compounds; Cyclononatetraenyl; Cyclooctatetraene; Docking; Ligands; Metal sheets; Metals; Palladium; Palladium-Cluster; Platinum; Sandwich-Komplexe; Unsaturated hydrocarbons
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201908850

The ligand‐unsupported accommodation of extra metal moieties in a sandwich complex is reported. Although it has been considered that the metal‐capacity of a metal sheet sandwich complex is strictly limited by the size of cyclic unsaturated hydrocarbon ligands, the M−M edge bonds in a metal sheet sandwich complex provide a ligand‐unsupported docking site for extra metal moieties, allowing expansion of metal‐capacity in sandwich complexes. The metal sheet sandwich complex [Pd4(μ4‐C8H8)(μ4‐C9H9)]+, in which the ligand‐based metal capacity is full in terms of the usage of all C=C moieties of the smaller carbocyclic ligand C8H8 in coordination, can accommodate extra M0{P(OPh)3}2 (M=Pd, Pt) moieties without coordinative assistance by either the C9H9 or the C8H8 ligand. Belegte Brote: Die Aufnahme von Metallresten in einem Sandwichkomplex, ohne Unterstützung der Liganden, wird vorgestellt. Der koordinativ ungesättigte Pd4‐Sandwichkomplex, in dem die Anzahl der Metallatome bereits die Kapazität der Liganden erreicht hat, nahm M0{P(OPh)3}2 (M=Pd0 oder Pt0) Reste an den Pd‐Pd‐Kanten auf. Durch die reversible Assoziation nullwertiger Metallreste bietet sich die Möglichkeit, Sandwichkomplexe als Metallträger zu nutzen.