The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT
Само за регистроване кориснике
2021
Аутори
Milovanović, Milan R.Boucher, Mélanie
Cornaton, Yann
Zarić, Snežana D.
Pfeffer, Michel
Djukic, Jean-Pierre
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
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/continu...um solvation enthalpies, that are suspected to arise from an unexpected explicit noncovalent interaction of PhCl with the components of the reaction.
Кључне речи:
Calorimetry / Density functional calculations / Insertion / Metallacycles / PalladiumИзвор:
European Journal of Inorganic Chemistry, 2021, 2021, 45, 4690-4699Издавач:
- Wiley
Финансирање / пројекти:
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200168 (Универзитет у Београду, Хемијски факултет) (RS-MESTD-inst-2020-200168)
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200288 (Иновациони центар Хемијског факултета у Београду доо) (RS-MESTD-inst-2020-200288)
DOI: 10.1002/ejic.202100750
ISSN: 1434-1948
WoS: 000719613600001
Scopus: 2-s2.0-85119157645
URI
https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.202100750C:\Users\Ana\Zotero\storage\ZAYTN3C5\Milovanović et al. - 2021 - The Thermochemistry of Alkyne Insertion into a Pal.pdf
C:\Users\Ana\Zotero\storage\JYEI976E\ejic.html
http://cherry.chem.bg.ac.rs/handle/123456789/4783
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Milovanović, Milan R. AU - Boucher, Mélanie AU - Cornaton, Yann AU - Zarić, Snežana D. AU - Pfeffer, Michel AU - Djukic, Jean-Pierre PY - 2021 UR - https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.202100750 UR - C:\Users\Ana\Zotero\storage\ZAYTN3C5\Milovanović et al. - 2021 - The Thermochemistry of Alkyne Insertion into a Pal.pdf UR - C:\Users\Ana\Zotero\storage\JYEI976E\ejic.html UR - http://cherry.chem.bg.ac.rs/handle/123456789/4783 AB - 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. PB - Wiley T2 - European Journal of Inorganic Chemistry T1 - The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT VL - 2021 IS - 45 SP - 4690 EP - 4699 DO - 10.1002/ejic.202100750 ER -
@article{ author = "Milovanović, Milan R. and Boucher, Mélanie and Cornaton, Yann and Zarić, Snežana D. and Pfeffer, Michel and Djukic, Jean-Pierre", year = "2021", 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.", publisher = "Wiley", journal = "European Journal of Inorganic Chemistry", title = "The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT", volume = "2021", number = "45", pages = "4690-4699", doi = "10.1002/ejic.202100750" }
Milovanović, M. R., Boucher, M., Cornaton, Y., Zarić, S. D., Pfeffer, M.,& Djukic, J.. (2021). The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT. in European Journal of Inorganic Chemistry Wiley., 2021(45), 4690-4699. https://doi.org/10.1002/ejic.202100750
Milovanović MR, Boucher M, Cornaton Y, Zarić SD, Pfeffer M, Djukic J. The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT. in European Journal of Inorganic Chemistry. 2021;2021(45):4690-4699. doi:10.1002/ejic.202100750 .
Milovanović, Milan R., Boucher, Mélanie, Cornaton, Yann, Zarić, Snežana D., Pfeffer, Michel, Djukic, Jean-Pierre, "The Thermochemistry of Alkyne Insertion into a Palladacycle Outlines the Solvation Conundrum in DFT" in European Journal of Inorganic Chemistry, 2021, no. 45 (2021):4690-4699, https://doi.org/10.1002/ejic.202100750 . .