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 . .