N‐Heterocyclic Phosphenium Complex of Manganese: Synthesis and Catalytic Activity in Ammonia Borane Dehydrogenation

• Published in: Chemistry : a European journal 2017-08, Vol.23 (48), p.11560-11569
• Main Authors: Gediga, Micheal, Feil, Christoph M., Schlindwein, Simon H., Bender, Johannes, Nieger, Martin, Gudat, Dietrich
• Format: Article
• Language: English
• Subjects: Activation; Ammonia; Anion exchange; Anion exchanging; Carbonyls; Catalysis; Catalysts; Catalytic activity; Chemical synthesis; Chemistry; Computer applications; Cyclohexene; Dehydrogenation; hydrogen transfer; Hydrogenation; Infrared spectroscopy; Irradiation; Ligands; Light emitting diodes; Magnetic resonance spectroscopy; Manganese; Metals; Metathesis; N-heterocyclic phosphenium complexes; Nitrogen; NMR spectroscopy; P ligands; Phosphine; Phosphorus; Protonation; reaction mechanisms; Regioselectivity; Single crystals; Spectroscopic analysis; Ultraviolet radiation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201701442

A neutral N‐heterocyclic phosphenium complex of manganese was synthesised by a metathesis approach and characterised by IR, NMR, and XRD studies. The short P−Mn distance suggests a substantial metal–ligand double bond character. Reaction with a hydride produced an anionic phosphine complex, which was also characterised by IR and NMR spectroscopy and, after anion exchange, a single‐crystal XRD study. Protonation of the anion occurs at the metal to yield a neutral phosphine metal carbonyl hydride, which releases dihydrogen upon irradiation with UV light. These reactions confirm the electrophilic nature of the phosphenium ligand and suggest that the title complex might undergo reactions displaying metal–ligand cooperativity. Surprisingly, reaction with ammonia borane (AB) did not proceed under transfer hydrogenation of the Mn=P double bond but through the catalytic dehydrogenation of AB. The phosphenium complex behaves here as a class II catalyst, which dehydrogenates AB to NH2BH2 that was trapped with cyclohexene. Computational model studies led to the identification of two possible catalytic cycles, which differ in the regioselectivity of the initial AB activation step. In one case, the activation proceeds as cooperative transfer hydrogenation of the Mn=P bond, whereas in the other case a H+/H− pair is transferred to the phosphorus atom and a nitrogen atom of the phosphenium unit, resulting in a ligand‐centred reaction in which the metal fragment acts merely as stabilising substituent. Unexpectedly, this pathway, which constitutes a new reaction mode for phosphenium complexes, seems to be better in accord with experimental findings on the course of the catalysis. Better than ever: A neutral N‐heterocyclic phosphenium complex of manganese reacts upon sequential transfer of a H−/H+ pair under formal hydrogenation of the Mn=P double bond and may accomplish the catalytic dehydrogenation of ammonia borane. Computational studies indicate that this reaction illustrates a new scheme of metal–ligand cooperativity in which the ligand adopts the role of the Lewis acidic reaction centre (see scheme).