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

Buss, Joshua A. and Hirahara, Masanari and Ueda, Yohei and Agapie, Theodor (2018) Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity. Angewandte Chemie International Edition, 57 (50). pp. 16329-16333. ISSN 1433-7851.

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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.

Item Type:Article
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URLURL TypeDescription
Buss, Joshua A.0000-0002-3347-8583
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. Manuscript received: July 19, 2018; Revised manuscript received: September 18, 2018; Accepted manuscript online: October 12, 2018; Version of record online: November 14, 2018. We thank Lawrence M. Henling and Dr. Michael K. Takase for crystallographic assistance and Dr. David VanderVelde for NMR expertise. T.A. is grateful for a Dreyfus fellowship and for NSF funding (CHE‐1151918 and CHE‐1800501), J.A.B. for an NSF graduate research fellowship, M.H. for funding from the Grant‐in‐Aid for Young Scientists (B) (17K18433), and Y.U. for financial support from the JSPS Research Fellowships for Young Scientists. We thank the Dow Next Generation Fund and the NSF (NSF‐1531940) for instrumentation. The authors declare no conflict of interest.
Funding AgencyGrant Number
Camille and Henry Dreyfus FoundationUNSPECIFIED
NSF CHE-1151918
NSF Graduate Research FellowshipUNSPECIFIED
Japan Society for the Promotion of Science (JSPS)17K18433
Dow Next Generation FundUNSPECIFIED
Subject Keywords:μ-Phosphide; μ-Phosphinidene; Thermochemistry; Proton Reduction; Molybdenum
Issue or Number:50
Record Number:CaltechAUTHORS:20181012-131902698
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Official Citation:J. A. Buss, M. Hirahara, Y. Ueda, T. Agapie, Angew. Chem. Int. Ed. 2018, 57, 16329
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90265
Deposited By: Tony Diaz
Deposited On:12 Oct 2018 20:27
Last Modified:03 Oct 2019 20:23

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