Accurate Prediction of IrH Bond Dissociation Enthalpies by Density Functional Theory Methods |
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Authors: | Yi Zhou Dingjia Liu Yao Fu Haizhu Yu Jing Shi |
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Affiliation: | 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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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? 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? H bond strengths has been examined on the basis of the previously reported Ir? 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? 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? H BDEs. We wish the present study could benefit future studies on the Ir‐H complexes involved organic reactions. |
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Keywords: | density functional theory Ir H bond dissociation enthalpy |
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