Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity

Abstract

AbstractA new series of low‐valent dinuclear molybdenum complexes bearing phosphido or phosphinidene bridging ligands was synthesized as a structural model of heterogeneous metal phosphide catalysts. Addition of acid to a monocationic Mo2‐μ‐P complex results in phosphide protonation, affording a dicationic Mo2‐μ‐PH species. Alternatively, reaction of an isoelectronic Mo2‐μ‐P precursor with LiBEt3H gives a Mo2H‐μ‐P complex. Mixing these species, one bearing a Mo−H and the other a P−H bond, results in facile H2 production at room temperature.