Determination of the best functional and basis sets for optimization of the structure of hypervalent iodines and calculation of their first and second bond dissociation enthalpies
Determination of the best functional and basis sets for optimization of the structure of hypervalent iodines and calculation of their first and second bond dissociation enthalpies
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DOI：
10.1002/poc.3961
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发表时间：
2019-08-01
影响因子：
1.8
通讯作者：
Nemoto, Tetsuhiro
中科院分区：
文献类型：
--
作者：
Matsumoto, Koki;Nakajima, Masaya;Nemoto, Tetsuhiro
高价碘在有机化学中有着广泛的应用，其最重要的特征是三中心四电子键。然而，关于它们的键离解焓（BDE）的测定却鲜有报道。因此，在许多情况下，溴化二苯醚是通过计算机计算来估算的。然而，计算的BDE值通常会根据功能和基组的选择而变化，准确评估三中心四电子键的最佳方法尚未确定。我们成功地确定了计算三中心四电子键的最佳泛函和基组，误差在0.79%和0.53标准差之内。使用最佳的功能和基组，计算了几个高价碘的第一和第二BDE，并作为苯取代基的影响进行了研究，在Hammett图中观察到负相关。此外，环高价碘中邻位取代基的影响也很显著。此外，还计算了高价碘的分解途径。计算得出的溴化二苯醚值通常因选择的泛函和基组而异。我们成功地确定了最佳的功能和基组计算的三中心四电子键的高价碘在0.79%的误差和0.53的标准偏差。利用最优泛函和基组，计算了几种高价碘的第一和第二BDE，并计算了高价碘的分解途径。
Hypervalent iodines are widely used in organic chemistry, and their most important feature is the three-center four-electron bond. However, there have been few reports on the measurement of their bond dissociation enthalpy (BDE). Therefore, in many cases, BDE is estimated by computational calculations. However, the value of a calculated BDE usually varies depending on the choice of functional and basis set, and the best method for making an accurate evaluation of the three-center four-electron bond has not been determined. We succeeded in determining the best functional and basis set to calculate the three-center four-electron bond to within 0.79% error and 0.53 standard deviation. Using the optimal functional and basis set, the first and second BDEs of several hypervalent iodines are calculated, and as the effect of benzene substituents was investigated, negative correlation was observed in the Hammett plot. In addition, the effect of ortho-substituent in cyclic hypervalent iodine was found to be significant. Furthermore, the decomposition route of hypervalent iodine is calculated. The value of a calculated BDE usually varies depending on the choice of functional and basis set. We succeeded in determining the best functional and basis sets to calculate the three-center four-electron bond of hypervalent iodine to within 0.79% error and 0.53 standard deviation. Using the optimal functional and basis sets, the first and second BDEs of several hypervalent iodines are calculated, and additionally, the decomposition route of hypervalent iodine is calculated.