Falkowski Dawid, Mikolajczyk Alicja, Skurski Piotr
Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, Gdańsk 80-308, Poland.
QSAR Lab Ltd., Trzy Lipy 3, Gdańsk 80-172, Poland.
J Phys Chem A. 2025 Apr 3;129(13):3032-3039. doi: 10.1021/acs.jpca.5c00568. Epub 2025 Mar 19.
The possibility of stabilizing reactive dimethylzinc through salt formation has been investigated using advanced electronic structure methods and flexible basis sets. It was found that the attachment of a Cl ion to dimethylzinc is thermodynamically favorable (with a Gibbs free reaction energy of -22.88 kcal/mol at room temperature), occurring without a kinetic barrier. The resulting anion is strongly electronically bound, with an excess electron binding energy of 4.306 eV. The subsequent attachment of Li or Na ions to this anion leads to the formation of ionic salts (CH)ZnClLi or (CH)ZnClNa. These salts, formed through this two-step process, are thermodynamically stable and represent stabilized forms of dimethylzinc, from which the pure dimethylzinc compound can be regenerated via the procedures suggested in this work. In addition to the structural characterization of these systems and a detailed analysis of the electronic structure of the (CH)ZnCl anion, which plays a key role in the described process, experimental approaches for realizing each transformation are also proposed.
已使用先进的电子结构方法和灵活的基组研究了通过盐形成来稳定活性二甲基锌的可能性。研究发现，一个氯离子与二甲基锌的结合在热力学上是有利的（在室温下吉布斯自由反应能为-22.88千卡/摩尔），且反应没有动力学障碍。生成的阴离子具有强烈的电子束缚，多余电子的结合能为4.306电子伏特。随后锂或钠离子与该阴离子结合会形成离子盐(CH₃)₂ZnClLi或(CH₃)₂ZnClNa。通过这两步过程形成的这些盐在热力学上是稳定的，代表了二甲基锌的稳定形式，可通过本工作中建议的程序从中再生出纯二甲基锌化合物。除了对这些体系进行结构表征以及对在所述过程中起关键作用的(CH₃)₂ZnCl阴离子的电子结构进行详细分析外，还提出了实现每种转化的实验方法。
