Joint Isotherm Calorimetric Titration–DFT Investigation of the Demethoxy-Amination of Fischer Carbenes
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 wi...th aniline.
Keywords:
Calorimetry / Carbenes / Chromium / Density functional theory / Molybdenum / TungstenSource:
Journal of Organometallic Chemistry, 2020, 929, 121582-Publisher:
- Elsevier
Funding / projects:
- Agence Nationale de la Recherche through the ANR-DFG grant COCOORDCHEM.
- Noncovalent interactions of pi-systems and their role in molecular recognition (RS-MESTD-Basic Research (BR or ON)-172065)
DOI: 10.1016/j.jorganchem.2020.121582
ISSN: 0022-328X
WoS: 000589931100008
Scopus: 2-s2.0-85093948232
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - 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 . .