Accurate Prediction of Ir[BOND]H Bond Dissociation Enthalpies by Density Functional Theory Methods

Authors

  • Yi Zhou,

    1. Department of Polymer Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
    2. Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China
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  • Dingjia Liu,

    1. Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China
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  • Yao Fu,

    1. Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China
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  • Haizhu Yu,

    Corresponding author
    1. Department of Polymer Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
    • Haizhu Yu, Department of Polymer Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China, Tel.: 0086-010-62334748; Fax: 0086-010-62334516

      Jing Shi, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China

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  • Jing Shi

    Corresponding author
    1. Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China
    • Haizhu Yu, Department of Polymer Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China, Tel.: 0086-010-62334748; Fax: 0086-010-62334516

      Jing Shi, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China

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Abstract

The iridium hydride complexes have been extensively used in organic reactions, such as oxidation and hydrogenation reactions. In many of these reactions, the dissociation or formation of Ir[BOND]H bond plays an important role in determining the overall reaction rates and yields. In the present study, the accuracy of different theoretical methods for prediction of Ir[BOND]H bond strengths has been examined on the basis of the previously reported Ir[BOND]H BDEs of 17 different complexes. Comparing the performance of different DFT functionals (e.g. B3LYP, TPSS, M06), different basis sets (including the different effective core potentials (ECP) on Ir and I atoms, and the total electron basis sets on the other atoms), and different solvation models (SMD, CPCM, and IEFPCM) in solution phase single point calculations, we found that the gas-phase calculation with TPSS/(LanL2DZ: 6-31G(d)) method is relatively more accurate than the other gas-phase calculation methods, and can well simulate the Ir[BOND]H BDEs in low-polarity solvents (such as chlorobenzene and dichloroethane). Finally, efforts were put in analyzing the structure-activity relationships between the ligand structure (around Ir center) and the Ir[BOND]H BDEs. We wish the present study could benefit future studies on the Ir-H complexes involved organic reactions.

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