Repositori URV

Identificador: imarina:9390036

Handle: https://hdl.handle.net/20.500.11797/imarina9390036

Autors:
Zhang, YujiePuiggali-Jou, JordiMullaliu, AngeloSole-Daura, AlbertCarbo, Jorge JParac-Vogt, Tatjana Nde Azambuja, Francisco

Resum:
The capricious reactivity and speciation of earth-abundant metals (EAM) hinder the mechanistic understanding essential to boost their efficiency and versatility in catalysis. Moreover, metal's solution chemistry and reactivity are conventionally controlled using organic ligands, while their fundamental chemistry in operando conditions is often overlooked. However, in this study, we showcase how a better understanding of in operando conditions may result in improved catalytic reactions. By assessing the composition and structure of active species for Zr-catalyzed direct amide bond formations under operating conditions, we discovered zirconium oxo clusters form quickly and are likely active species in the reactions. Formation of these clusters dismisses the use of additional organic ligands, inert atmosphere, anhydrous solvents, or even water scavenging to provide amides in good to excellent yields. More specifically, dodeca- and hexazirconium oxo clusters (Zr-12 and Zr-6, respectively) rapidly form from commercial, readily available Zr salts under reaction conditions known to afford amides directly from nonactivated carboxylic acid and amine substrates. Extended X-ray absorption fine structure (EXAFS) experiments confirm the presence of oxo clusters in solution throughout the reaction, while their key role in the mechanism is supported by an in-depth computational study employing density functional theory (DFT) and molecular dynamics (MD) methods. These results underline the value of (earth-abundant) metals' intrinsic solution chemistry to transformative mechanistic understanding and to enhance the sustainability of organic transformations.