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Hierarchy of Commonly Used DFT Methods for Predicting the Thermochemistry of Rh-Mediated Chemical Transformations

机译：用于预测Rh介导的化学转化的热化学的常用DFT方法的层次

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The accuracy and reliability of 17 commonly used density functionals in conjunction with Poisson–Boltzmann finite solvation model were gauged for predicting the free energy of Rh(I)- and Rh(III)-mediated chemical transformations such as ligand exchange, hydride elimination, dihydrogen elimination, chloride affinity, and silyl hydride bond activation reactions. In total, six Rh-mediated reactions were examined, and the computed density functional theory results were then subjected to comparison with the experimentally reported values. For reaction A, involving replacement of N2 with η2-H2 over Rh(I), MPWB1K-D3, B3PW91, B3LYP, and BHandHYLP emerged to be the best functionals of all the tested methods in terms of their deviations ≤2 kcal mol–1 from experimental data. For reaction B, in which exchange of η2-C2H4 with N2 over Rh(I) takes place, MPWB1K-D3 and M06-2X-D3 functionals performed the best, while as for reaction C (hydride elimination reaction in Rh(III) complex), it is PBE functional that showed impressive performance. Similarly, for reaction D (H2 elimination reaction in Rh(III) complex), PBE0-D3 and PBE-D3 showed exceptional results compared to other functionals. For reaction E (H2O/Cl– exchange), the PBE0 again shows impressive performance as compared to other functionals. For reaction F (Si–H activation), M06-2X-D3, PBE0-D3, and MPWB1K-D3 functionals are undoubtedly the best functionals. Overall, PBE0-D3 and MPWB1K-D3 functionals were impressive in all cases with lowest mean unsigned errors (3.2 and 3.4 kcal mol–1, respectively) with respect to experimental Gibbs free energies. Thus, these two functionals are recommended for studying Rh-mediated chemical transformations.
机译：测量了17种常用密度泛函和Poisson-Boltzmann有限溶剂化模型的准确性和可靠性，以预测Rh（I）和Rh（III）介导的化学转化（例如配体交换，氢化物消除，二氢）的自由能消除，氯化物亲和力和甲硅烷基氢化物键活化反应。总共检查了六个Rh介导的反应，然后将计算出的密度泛函理论结果与实验报告的值进行比较。对于反应A，涉及用Rh（I）上的η2-H2替代N2，MPWB1K-D3，B3PW91，B3LYP和BHandHYLP的偏差≤2kcal mol–1成为了所有测试方法中的最佳功能。根据实验数据对于反应B（其中η2-C2H4与N2在Rh（I）上进行交换），MPWB1K-D3和M06-2X-D3官能团表现最佳，而反应C（Rh（III）络合物中的氢化物消除反应） ），PBE功能显示了令人印象深刻的性能。同样，对于反应D（Rh（III）络合物中的H2消除反应），与其他功能相比，PBE0-D3和PBE-D3显示出优异的结果。对于反应E（H2O / Cl–交换），与其他功能相比，PBE0再次显示出令人印象深刻的性能。对于反应F（Si–H活化），M06-2X-D3，PBE0-D3和MPWB1K-D3无疑是最好的功能。总体而言，相对于实验吉布斯自由能，PBE0-D3和MPWB1K-D3在所有情况下均具有令人印象深刻的平均无符号误差最低（分别为3.2和3.4 kcal mol-1）。因此，推荐这两个功能用于研究Rh介导的化学转化。

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