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

Autor: Queyriaux N; LCC-CNRS, Université de Toulouse, CNRS, UPS 205 Route de Narbonne, BP44099 F-31077 Toulouse Cedex 4 France antoine.simonneau@lcc-toulouse.fr nicolas.queyriaux@lcc-toulouse.fr., Cabrera-Trujillo JJ; CNRS/UPPA, IPREM UMR 5254, E2S-UPPA, Hélioparc 2 Avenue du Président Angot 64053 Pau Cedex 09 France karinne.miqueu@univ-pau.fr., Durvin N; LCC-CNRS, Université de Toulouse, CNRS, UPS 205 Route de Narbonne, BP44099 F-31077 Toulouse Cedex 4 France antoine.simonneau@lcc-toulouse.fr nicolas.queyriaux@lcc-toulouse.fr., Vendier L; LCC-CNRS, Université de Toulouse, CNRS, UPS 205 Route de Narbonne, BP44099 F-31077 Toulouse Cedex 4 France antoine.simonneau@lcc-toulouse.fr nicolas.queyriaux@lcc-toulouse.fr., Miqueu K; CNRS/UPPA, IPREM UMR 5254, E2S-UPPA, Hélioparc 2 Avenue du Président Angot 64053 Pau Cedex 09 France karinne.miqueu@univ-pau.fr., Simonneau A; LCC-CNRS, Université de Toulouse, CNRS, UPS 205 Route de Narbonne, BP44099 F-31077 Toulouse Cedex 4 France antoine.simonneau@lcc-toulouse.fr nicolas.queyriaux@lcc-toulouse.fr.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2024 Nov 18; Vol. 15 (48), pp. 20582-20589. Date of Electronic Publication: 2024 Nov 18 (Print Publication: 2024).
DOI: 10.1039/d4sc04345f
Abstrakt: The cationic molybdenum pentahydride complex [MoH 5 (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 CO 2 into a metal-hydride bond is observed, resulting in the formation of the expected formate complex, [MoH 2 (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.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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