Repositori institucional URV
| URV's Author/s: | Carbó Martin, Jorge Juan / Solé Daura, Albert |
| Author, as appears in the article.: | Zhang, Yujie; Puiggali-Jou, Jordi; Mullaliu, Angelo; Sole-Daura, Albert; Carbo, Jorge J; Parac-Vogt, Tatjana N; de Azambuja, Francisco |
| Author's mail: | j.carbo@urv.cat |
| Author identifier: | 0000-0002-3945-6721 |
| Journal publication year: | 2024 |
| Publication Type: | Journal Publications |
| APA: | Zhang, Yujie; Puiggali-Jou, Jordi; Mullaliu, Angelo; Sole-Daura, Albert; Carbo, Jorge J; Parac-Vogt, Tatjana N; de Azambuja, Francisco (2024). Mechanism Insight into Direct Amidation Catalyzed by Zr Salts: Evidence of Zr Oxo Clusters as Active Species. Inorganic Chemistry, 63(43), 20347-20360. DOI: 10.1021/acs.inorgchem.4c02526 |
| Papper original source: | Inorganic Chemistry. 63 (43): 20347-20360 |
| Abstract: | 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. |
| Article's DOI: | 10.1021/acs.inorgchem.4c02526 |
| Link to the original source: | https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c02526 |
| Papper version: | info:eu-repo/semantics/publishedVersion |
| licence for use: | https://creativecommons.org/licenses/by/3.0/es/ |
| Department: | Química Física i Inorgànica |
| Licence document URL: | https://repositori.urv.cat/ca/proteccio-de-dades/ |
| Thematic Areas: | Astronomia / física Biotecnología Chemistry (miscellaneous) Chemistry, inorganic & nuclear Ciências agrárias i Ciências biológicas i Ciências biológicas ii Ciências biológicas iii Engenharias i Engenharias ii Engenharias iii Farmacia General medicine Inorganic chemistry Interdisciplinar Materiais Medicina i Physical and theoretical chemistry Química |
| Keywords: | Augmented basis-sets Body distribution-functions Condensed matter Densit Direct amide formation Dynamics Molecular-orbital methods Nonactivated carboxylic-acids Peptide-bond hydrolysis Ray-absorption spectroscopy |
| Entity: | Universitat Rovira i Virgili |
| Record's date: | 2024-11-16 |
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