Queyriaux Nicolas, Cabrera-Trujillo Jorge J, Durvin Nina, Vendier Laure, Miqueu Karinne, Simonneau Antoine
LCC-CNRS, Université de Toulouse, CNRS, UPS 205 Route de Narbonne, BP44099 F-31077 Toulouse Cedex 4 France
CNRS/UPPA, IPREM UMR 5254, E2S-UPPA, Hélioparc 2 Avenue du Président Angot 64053 Pau Cedex 09 France
Chem Sci. 2024 Nov 18;15(48):20582-20589. doi: 10.1039/d4sc04345f. eCollection 2024 Dec 11.
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.
阳离子五氢化钼配合物[MoH(depe)]（depe = 1,2 - 双（二乙基膦基）乙烷）被证明能与二氧化碳发生两个连续反应。在初始的室温过程中，观察到CO经典地插入金属 - 氢化物键中，生成预期的甲酸酯配合物[MoH(HCOO)(depe)]。在温度高于100°C时引发进一步反应。确实观察到完全转化为两种新配合物，这是由于二氧化碳的C - O键发生形式上的断裂，生成了[MoH(CO)(depe)]和[MoO(HCOO)(depe)]。在没有配体协助的情况下这种金属氢化物反应是前所未有的，已经通过实验和计算手段相结合的方式对这种反应进行了全面研究，目的是阐明控制这一过程的潜在机制。
