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Updated: Feb 4, 2026

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Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride-Proton Isomerism, and HER Reactivity
Joshua A Buss1, Masanari Hirahara1, Yohei Ueda1
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA.
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 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 LiBEt3 H gives a Mo2 H-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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