Influence of Ancillary Ligands on the Kinetics and the Thermodynamics of H2 Addition to IrXH2(PR3)2 (X = Cl, Br, I and R = H, Me): Comparison between Density Functional Theory and Perturbation Theory

The electronic influence of ancillary ligands on the addition of H 2 to IrXH 2 (PR 3 ) 2 (X = Cl, Br, I; R = H, Me) has been studied. The reaction enthalpy and the activation energy for the formation of a molecular dihydrogen complex have been computed. Results from ab initio MO perturbation theory (MP2) and density functional theory (B3LYP) are compared. The calculated geometries are in good agreement with the experimental results for IrClH 2 (P t Bu 2 Me) 2 and IrIH 2 (H 2 )(P i Pr 3 ) 2 . The binding energy of H 2 is underestimated by B3LYP, while it is overestimated by MP2. The results are improved by modeling the phosphine with PMe 3 instead of PH 3 . The reaction enthalpies and the activation energies are in excellent agreement with the experimental data and follow the experimental trend along the halide series. The transition state for the addition corresponds to the deformation of the unsaturated fragment IrXH 2 (PH 3 ) 2 with almost no interaction with the incoming H 2 molecule. The trends for the activation and thermodynamic enthalpies among the halide series are rationalized in terms of π donor ability of the halides and variable strength of the trans influence of the hydride ligand.