Article Dans Une Revue Chemical Science Année : 2024

Reactivity of metal hydrides with CO2 : going beyond formate with a high-valent cationic pentahydride Mo(VI ) complex

Résumé

The cationic molybdenum pentahydride complex [MoH5(depe)2]+ (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 CO2 into a metal-hydride bond is observed, resulting in the formation of the expected formate complex, [MoH2(HCOO)(depe)2]+. 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)2(depe)2]+ and [MoO(HCOO)(depe)2]+. 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.

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hal-04826899 , version 1 (09-12-2024)

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Nicolas Queyriaux, Jorge Cabrera-Trujillo, Nina Durvin, Laure Vendier, Karinne Miqueu, et al.. Reactivity of metal hydrides with CO2 : going beyond formate with a high-valent cationic pentahydride Mo(VI ) complex. Chemical Science, 2024, 15 (48), pp.20582-20589. ⟨10.1039/d4sc04345f⟩. ⟨hal-04826899⟩
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