Relating Bond Strength and Nature to the Thermodynamic Stability of Hypervalent Togni‐Type Iodine Compounds
Relating Bond Strength and Nature to the Thermodynamic Stability of Hypervalent Togni‐Type Iodine Compounds
复制标题
高价 Togni 型碘化合物的键强度和性质与热力学稳定性的关系
DOI：
10.1002/cplu.202100285
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发表时间：
2021
期刊：
影响因子：
3.4
通讯作者：
Kraka, Elfi
中科院分区：
文献类型：
--
作者：
Oliveira, Vytor Pinheiro;Marcial, Bruna Luana;Machado, Francisco B. C.;Kraka, Elfi
在M062 X/def 2-TZVP（D）理论水平上，在用SMD连续溶剂模型描述的乙腈中研究了一组32种Togni-样试剂的键强度和性质，以合理化不同构象中负责其热力学稳定性的主要因素，以及三氟甲基化能力。对于键强度的评估，我们利用本地拉伸力常数和相关的键强度顺序，补充与本地功能的电子密度访问的债券的性质。键离解能从31.6至79.9千卡/摩尔变化，这取决于极化功率的配体反式CF 3。 基于对密度的拉普拉斯算子的分析，我们提出电荷位移键特征在所研究的分子的稳定性中起着重要的作用，特别是对于那些含有I-O键的分子。提供了关于反式影响和微调这些试剂稳定性的可能方法的新见解。
The bond strength and nature of a set of 32 Togni‐like reagents have been investigated at the M062X/def2‐TZVP(D) level of theory in acetonitrile described with the SMD continuum solvent model, to rationalize the main factors responsible for their thermodynamic stability in different conformations, and trifluoromethylation capabilities. For the assessment of bond strength, we utilized local stretching force constants and associated bond strength orders, complemented with local features of the electron density to access the nature of the bonds. Bond dissociation energies varied from 31.6 to 79.9 kcal/mol depending on the polarizing power of the ligand trans to CF3. Based on the analysis of the Laplacian of the density, we propose that the charge‐shift bond character plays an important role in the stability of the molecules studied, especially for those containing I−O bonds. New insights on the trans influence and on possible ways to fine‐tune the stability of these reagents are provided.