2020
DOI: 10.1016/j.jorganchem.2020.121582
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Joint Isotherm Calorimetric Titration–DFT Investigation of the Demethoxy-Amination of Fischer Carbenes

Abstract: Enthalpies of amino-demethoxylation of Fischer carbenes measured in PhCl are mostly metal independent  ITC experiments carried out in chlorobenzene give reaction enthalpies consistent with static DFT-D calculations that assume implicit solvation

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Cited by 2 publications
(6 citation statements)
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“…There exist occurrences of good match between COSMO [103] (or other continuous screening solvation models)/DFT-D computed thermochemistry parameters with ITC data for systems implying neutral molecules (or bearing highly delocalized charges). [118][119][120][121] However, significant discrepancies have been often reported for chemical reactions involving salts, [122,123] in which the counter ion is systematically omitted in DFT calculations and the solvent happens to be a discrete actor. The question of solvation addressed using COSMO [103] either fully implicitly or with explicit amount of solvent applied to isolated ions may reputedly produce inaccurate solvation energy contributions.…”
Section: Influence Of Solvation and Of The Pair-wise Versus Many-body...mentioning
confidence: 99%
“…There exist occurrences of good match between COSMO [103] (or other continuous screening solvation models)/DFT-D computed thermochemistry parameters with ITC data for systems implying neutral molecules (or bearing highly delocalized charges). [118][119][120][121] However, significant discrepancies have been often reported for chemical reactions involving salts, [122,123] in which the counter ion is systematically omitted in DFT calculations and the solvent happens to be a discrete actor. The question of solvation addressed using COSMO [103] either fully implicitly or with explicit amount of solvent applied to isolated ions may reputedly produce inaccurate solvation energy contributions.…”
Section: Influence Of Solvation and Of The Pair-wise Versus Many-body...mentioning
confidence: 99%
“…[4] ITC is a powerful tool to investigate pre-catalyst activation and probe mechanistic schemes by static DFT. [4a] Furthermore, ITC can be used to extract kinetic information [5] , which requires nonetheless to back all ITC experiments with reaction monitoring by other spectroscopic means. Static DFT methods associated to a continuum solvation model remain to date one of the most time-effective expedient to draw energy profiles of reactions, [6] although most continuum (implicit) solvation models have crippling limitations.…”
Section: Introductionmentioning
confidence: 99%
“…[4] ITC is a powerful tool to investigate pre-catalyst activation and probe mechanistic schemes by static DFT. [4a] Furthermore, ITC can be used to extract kinetic information, [5] which requires nonetheless to back all ITC experiments with reaction monitoring by other spectroscopic means.…”
Section: Introductionmentioning
confidence: 99%
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