Mohammad Ameskal, Lionel Magna, Juan M. Asensio, Pascal Raybaud
{"title":"揭示丁二烯单烷氧羰基化的机理:碱的作用是什么?","authors":"Mohammad Ameskal, Lionel Magna, Juan M. Asensio, Pascal Raybaud","doi":"10.1016/j.jcat.2025.116235","DOIUrl":null,"url":null,"abstract":"<div><div>The mechanism of catalytic alkoxycarbonylation of alkenes has been extensively studied and it is generally accepted that it elapses through three elementary steps: (i) alkene insertion into a Pd<img>H bond, (ii) carbonylation, and (iii) alcoholysis. In the case of butadiene methoxycarbonylation catalyzed by [Pd(d<sup>t</sup>bpx)H]<sup>+</sup>, we have identified the formation of a highly stable Pd(<em>η</em><sup>3</sup>-allyl) intermediate by Density Functional Theory (DFT) calculations and Nuclear Magnetic Resonance (NMR). This intermediate makes the apparent kinetic barrier of the mechanism incompatible with experimental observations (ca. 200 kJ·mol<sup>−1</sup>). Upon coupling DFT calculations and experimental analysis, we proposed a revised mechanism founded on a “base assisted” pathway where the mono-alkoxycarbonylation of dienes exhibits a significantly decreased free energy of activation (ca. 100 kJ mol<sup>−1</sup>). Hence, we proposed that the base coming from the Pd precursor is non-innocent and participates in the reaction upon acting as proton shuttle during the alcoholysis step. By considering various acid/base pairs, we further refined these findings and demonstrated that an optimum balance between the acid and the base must be found, regarding strengths and concentrations, to maximize the catalytic activity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116235"},"PeriodicalIF":6.5000,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unravelling the mechanism for the mono-alkoxycarbonylation of butadiene: what is the role of the base?\",\"authors\":\"Mohammad Ameskal, Lionel Magna, Juan M. Asensio, Pascal Raybaud\",\"doi\":\"10.1016/j.jcat.2025.116235\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The mechanism of catalytic alkoxycarbonylation of alkenes has been extensively studied and it is generally accepted that it elapses through three elementary steps: (i) alkene insertion into a Pd<img>H bond, (ii) carbonylation, and (iii) alcoholysis. In the case of butadiene methoxycarbonylation catalyzed by [Pd(d<sup>t</sup>bpx)H]<sup>+</sup>, we have identified the formation of a highly stable Pd(<em>η</em><sup>3</sup>-allyl) intermediate by Density Functional Theory (DFT) calculations and Nuclear Magnetic Resonance (NMR). This intermediate makes the apparent kinetic barrier of the mechanism incompatible with experimental observations (ca. 200 kJ·mol<sup>−1</sup>). Upon coupling DFT calculations and experimental analysis, we proposed a revised mechanism founded on a “base assisted” pathway where the mono-alkoxycarbonylation of dienes exhibits a significantly decreased free energy of activation (ca. 100 kJ mol<sup>−1</sup>). Hence, we proposed that the base coming from the Pd precursor is non-innocent and participates in the reaction upon acting as proton shuttle during the alcoholysis step. By considering various acid/base pairs, we further refined these findings and demonstrated that an optimum balance between the acid and the base must be found, regarding strengths and concentrations, to maximize the catalytic activity.</div></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":\"450 \",\"pages\":\"Article 116235\"},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2025-05-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951725003008\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951725003008","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Unravelling the mechanism for the mono-alkoxycarbonylation of butadiene: what is the role of the base?
The mechanism of catalytic alkoxycarbonylation of alkenes has been extensively studied and it is generally accepted that it elapses through three elementary steps: (i) alkene insertion into a PdH bond, (ii) carbonylation, and (iii) alcoholysis. In the case of butadiene methoxycarbonylation catalyzed by [Pd(dtbpx)H]+, we have identified the formation of a highly stable Pd(η3-allyl) intermediate by Density Functional Theory (DFT) calculations and Nuclear Magnetic Resonance (NMR). This intermediate makes the apparent kinetic barrier of the mechanism incompatible with experimental observations (ca. 200 kJ·mol−1). Upon coupling DFT calculations and experimental analysis, we proposed a revised mechanism founded on a “base assisted” pathway where the mono-alkoxycarbonylation of dienes exhibits a significantly decreased free energy of activation (ca. 100 kJ mol−1). Hence, we proposed that the base coming from the Pd precursor is non-innocent and participates in the reaction upon acting as proton shuttle during the alcoholysis step. By considering various acid/base pairs, we further refined these findings and demonstrated that an optimum balance between the acid and the base must be found, regarding strengths and concentrations, to maximize the catalytic activity.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.