| Autor: |
Shahbaz Ahmad, Ellis Crawford, Muhammad Bilal, Johannes G. de Vries, Michael Bühl |
| Přispěvatelé: |
University of St Andrews. EaSTCHEM, University of St Andrews. School of Chemistry |
| Jazyk: |
angličtina |
| Rok vydání: |
2023 |
| Předmět: |
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| Popis: |
Authors thank EaStCHEM and the School of Chemistry for their support. The detailed mechanism for ruthenium-catalysed selective reductionof cardanol derivatives by transfer hydrogenation has been fully characterisedat the B3PW91-D3/ECP2/PCM//B3PW91/ECP1 level of density functional theory. Theexplored catalytic cycle involved the hydrogenation of the triene cardanolgiving the diene product through a highly stable η3-allylicintermediate via a kinetic barrier of 29.1 kcal mol−1, whichfollowed further hydrogenation leading to a more stable η3-allylicintermediate. The further reduction to the cardanol monoene product required anoverall barrier of 29.2 kcal mol−1, which offers a rationale for therequirement of elevated temperatures (refluxing isopropanol). The computedoverall barrier of 46.6 kcal mol−1 to accommodate a fully saturatedproduct is unsurmountable— in good agreement with the experiment, where no suchfull hydrogenation is observed, and rationalising the 100% selectivity towardsthe monoene product. Publisher PDF |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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