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Accurate Prediction of IrH Bond Dissociation Enthalpies by Density Functional Theory Methods
Author(s) -
Zhou Yi,
Liu Dingjia,
Fu Yao,
Yu Haizhu,
Shi Jing
Publication year - 2014
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201400015
Subject(s) - chemistry , chlorobenzene , bond dissociation energy , density functional theory , dissociation (chemistry) , iridium , hydride , computational chemistry , solvation , molecule , organic chemistry , catalysis , metal
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 IrH 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 IrH bond strengths has been examined on the basis of the previously reported IrH 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 IrH 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 IrH BDEs. We wish the present study could benefit future studies on the Ir‐H complexes involved organic reactions.