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Bifunctional Metal–Ligand Catalysis: Hydrogenations and New Reactions within the Metal–(Di)amine Scaffold


  • This work was supported by the Fonds der Chemischen Industrie. Abbreviations within this article: S/C=ratio of substrate to catalyst, TON=total turnover number, binap=2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl. For simplicity, in Schemes 1 and 3 the ligands 1,2-diphenylethylenediamine and η6-cymene are depicted as ethylenediamine and benzene, respectively.


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No metal–substrate interactions: A transition-metal complex of a primary amine can serve as an efficient bifunctional metal–ligand catalyst that functions without direct interaction of the metal and the substrate. The example shows the transition-state structure of the enantioselective reduction of acetophenone at the molecular surface of a ruthenium hydride complex bearing a diamine with one free NH2 group (O red, Ru green, N blue).

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