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Joint Isotherm Calorimetric Titration–DFT Investigation of the Demethoxy-Amination of Fischer Carbenes
Journal of Organometallic Chemistry ( IF 2.1 ) Pub Date : 2020-10-17 , DOI: 10.1016/j.jorganchem.2020.121582
Milan R. Milovanović , Snežana D. Zarić , Yann Cornaton , Jean-Pierre Djukic

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.



中文翻译:

联合等温量热滴定-费托卡宾糖的脱甲氧基胺化的DFT研究

三种苄基胺,苯胺和3-吡咯啉胺在理论上进行了实验研究,研究了三种甲氧基菲舍尔卡宾,五羰基(苯基甲氧基亚烷基)铬(0),钼(0)和钨(0)的氨解热化学。反应焓全部通过在298.15 K下的氯苯中的等温量热滴定法(ITC)确定,这几乎提供了所有情况下的Δr H值。大于-15kcal / mol,表明除了苯胺以外的所有胺在能量上有利的转化。没有发现反应焓对卡宾配合物的金属原子的性质有显着的依赖性。进一步的ITC实验证实了胺中的部分二级反应。发现所有COSMO-DFT计算的反应焓(跨度-5.5 kcal / mol至-20 kcal / mol)与实验值非常吻合,而计算的吉布斯自由能表明,除一种反应外,所有反应的自发过程与苯胺。

更新日期:2020-10-30
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