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The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT
dc.creator | Milovanović, Milan R. | |
dc.creator | Boucher, Mélanie | |
dc.creator | Cornaton, Yann | |
dc.creator | Zarić, Snežana D. | |
dc.creator | Pfeffer, Michel | |
dc.creator | Djukic, Jean-Pierre | |
dc.date.accessioned | 2021-12-02T12:23:12Z | |
dc.date.available | 2021-12-02T12:23:12Z | |
dc.date.issued | 2021 | |
dc.identifier.issn | 1434-1948 | |
dc.identifier.uri | https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.202100750 | |
dc.identifier.uri | C:\Users\Ana\Zotero\storage\ZAYTN3C5\Milovanović et al. - 2021 - The Thermochemistry of Alkyne Insertion into a Pal.pdf | |
dc.identifier.uri | C:\Users\Ana\Zotero\storage\JYEI976E\ejic.html | |
dc.identifier.uri | http://cherry.chem.bg.ac.rs/handle/123456789/4783 | |
dc.description.abstract | In an effort to determine the thermochemistry of established organometallic transformation, the well documented reaction of alkynes with a palladacycle was investigated by isothermal titration calorimetry (ITC). Although the mechanism of the insertion of unsaturated substrates into the Pd−C bond of cyclopalladated compounds is known, no information is available so far about their thermochemistry. The enthalpies of the reactions of Ph−C≡C−Ph and MeOC(O)−C≡C(O)COMe with the bisacetonitrilo salt of the N,N-benzylamine palladacycle were determined by ITC in chlorobenzene after having optimized the conditions to ensure that only the double and a single insertion of alkynes were occurring respectively. The reaction energy profile established by DFT for the double insertion process involving Ph−C≡C−Ph confirmed earlier conclusions on the rate determining character of the first insertion. Further computations of reaction enthalpies reveal significant discrepancies between ITC and DFT-D/continuum solvation enthalpies, that are suspected to arise from an unexpected explicit noncovalent interaction of PhCl with the components of the reaction. | |
dc.language | en | |
dc.publisher | Wiley | |
dc.relation | info:eu-repo/grantAgreement/MESTD/inst-2020/200168/RS// | |
dc.relation | info:eu-repo/grantAgreement/MESTD/inst-2020/200288/RS// | |
dc.rights | restrictedAccess | |
dc.source | European Journal of Inorganic Chemistry | |
dc.subject | Calorimetry | |
dc.subject | Density functional calculations | |
dc.subject | Insertion | |
dc.subject | Metallacycles | |
dc.subject | Palladium | |
dc.title | The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT | |
dc.type | article | en |
dc.rights.license | ARR | |
dc.citation.volume | 2021 | |
dc.citation.issue | 45 | |
dc.citation.spage | 4690 | |
dc.citation.epage | 4699 | |
dc.identifier.wos | 000719613600001 | |
dc.identifier.doi | 10.1002/ejic.202100750 | |
dc.citation.rank | M22~ | |
dc.type.version | publishedVersion | |
dc.identifier.scopus | 2-s2.0-85119157645 |