TY  - 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 . .

TY  - JOUR
AU  - Milovanović, Milan R.
AU  - Zarić, Snežana D.
AU  - Cornaton, Yann
AU  - Đukić, Jean-Pierre
PY  - 2020
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/4267
AB  - The thermochemistry of the aminolysis of three methoxy Fischer carbenes, pentacarbonyl(phenylmethoxyalkylidene)chromium(0), molybdenum(0) and tungsten(0), was studied experimentally and theoretically with three amines, namely benzylamine, aniline and 3-pyrroline. Enthalpies of reactions were all determined by Isotherm Calorimetric Titration (ITC) in chlorobenzene at 298.15 K, which provided in almost all cases values of ΔrH larger than -15 kcal/mol suggesting energetically favourable transformations for all amines except aniline. No significant dependence of the enthalpy of reaction upon the nature of the metal atom of the carbene complex was found. Further ITC experiments confirmed the partial second-order reaction in amine. All COSMO-DFT computed enthalpies of reaction (spanning ca. -5.5 kcal/mol up to -20 kcal/mol) were found to be in excellent agreement with experimental values, while calculated Gibbs free energies suggested spontaneous processes for all reactions except the one with aniline.
PB  - Elsevier
T2  - Journal of Organometallic Chemistry
T1  - Joint Isotherm Calorimetric Titration–DFT Investigation of the Demethoxy-Amination of Fischer Carbenes
VL  - 929
SP  - 121582
DO  - 10.1016/j.jorganchem.2020.121582
ER  - 

@article{
author = "Milovanović, Milan R. and Zarić, Snežana D. and Cornaton, Yann and Đukić, Jean-Pierre",
year = "2020",
abstract = "The thermochemistry of the aminolysis of three methoxy Fischer carbenes, pentacarbonyl(phenylmethoxyalkylidene)chromium(0), molybdenum(0) and tungsten(0), was studied experimentally and theoretically with three amines, namely benzylamine, aniline and 3-pyrroline. Enthalpies of reactions were all determined by Isotherm Calorimetric Titration (ITC) in chlorobenzene at 298.15 K, which provided in almost all cases values of ΔrH larger than -15 kcal/mol suggesting energetically favourable transformations for all amines except aniline. No significant dependence of the enthalpy of reaction upon the nature of the metal atom of the carbene complex was found. Further ITC experiments confirmed the partial second-order reaction in amine. All COSMO-DFT computed enthalpies of reaction (spanning ca. -5.5 kcal/mol up to -20 kcal/mol) were found to be in excellent agreement with experimental values, while calculated Gibbs free energies suggested spontaneous processes for all reactions except the one with aniline.",
publisher = "Elsevier",
journal = "Journal of Organometallic Chemistry",
title = "Joint Isotherm Calorimetric Titration–DFT Investigation of the Demethoxy-Amination of Fischer Carbenes",
volume = "929",
pages = "121582",
doi = "10.1016/j.jorganchem.2020.121582"
}

Milovanović, M. R., Zarić, S. D., Cornaton, Y.,& Đukić, J.. (2020). Joint Isotherm Calorimetric Titration–DFT Investigation of the Demethoxy-Amination of Fischer Carbenes. in Journal of Organometallic Chemistry
Elsevier., 929, 121582.
https://doi.org/10.1016/j.jorganchem.2020.121582

Milovanović MR, Zarić SD, Cornaton Y, Đukić J. Joint Isotherm Calorimetric Titration–DFT Investigation of the Demethoxy-Amination of Fischer Carbenes. in Journal of Organometallic Chemistry. 2020;929:121582.
doi:10.1016/j.jorganchem.2020.121582 .

Milovanović, Milan R., Zarić, Snežana D., Cornaton, Yann, Đukić, Jean-Pierre, "Joint Isotherm Calorimetric Titration–DFT Investigation of the Demethoxy-Amination of Fischer Carbenes" in Journal of Organometallic Chemistry, 929 (2020):121582,
https://doi.org/10.1016/j.jorganchem.2020.121582 . .