Reactivity of metal hydrides with CO 2 : going beyond formate with a high-valent cationic pentahydride Mo(vi) complex

The cationic molybdenum pentahydride complex [MoH (depe) ] (depe = 1,2-bis(diethylphosphino)ethane) is shown to undergo two consecutive reactions with carbon dioxide. In the initial, room-temperature process, classical insertion of CO into a metal-hydride bond is observed, resulting in the formation...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2024-12, Vol.15 (48), p.20582
Main Authors: Queyriaux, Nicolas, Cabrera-Trujillo, Jorge J, Durvin, Nina, Vendier, Laure, Miqueu, Karinne, Simonneau, Antoine
Format: Article
Language:English
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Summary:The cationic molybdenum pentahydride complex [MoH (depe) ] (depe = 1,2-bis(diethylphosphino)ethane) is shown to undergo two consecutive reactions with carbon dioxide. In the initial, room-temperature process, classical insertion of CO into a metal-hydride bond is observed, resulting in the formation of the expected formate complex, [MoH (HCOO)(depe) ] . Further reactivity is triggered at temperature above 100 °C. Complete conversion into two new complexes is indeed observed, resulting from the formal cleavage of a C-O bond of carbon dioxide, [MoH(CO) (depe) ] and [MoO(HCOO)(depe) ] . Unprecedented in the absence of ligand assistance, such metal hydride reactivity has been comprehensively studied by a combination of experimental and computational means with the aim of elucidating the underlying mechanism that governs this process.
ISSN:2041-6520
2041-6539
DOI:10.1039/D4SC04345F