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

Abstract

A 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 Mo_2‐μ‐P complex results in phosphide protonation, affording a dicationic Mo_2‐μ‐PH species. Alternatively, reaction of an isoelectronic Mo_2‐μ‐P precursor with LiBEt_3H gives a Mo_2H‐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.

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