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 NH BH 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.

Subsequent reactions of a neutral phosphenium complex of Mn with H− and H+ sources resulted in a stoichiometric H2 addition to the Mn=P double bond, which can be reversed upon thermal or photochemical excitation. In contrast, in the reaction with NH3BH3, the same complex acted as dehydrogenation catalyst. DFT studies suggested to explain this transformation as a ligand‐centred process, in which the H+/H− pair is picked up by the phosphenium ligand and the metal is mainly a spectator. Apart from being the first application of a phosphenium complex in catalysis, this discovery adds a new twist to the further development of ligand‐centred reactivity and the use of metal complexes in catalysis. More information can be found in the Full Paper by D. Gudat et al. on page 11560.