Density Functional Theory Study on the ¹⁹³Ir Mössbauer Spectroscopic Parameters of Vaska's Complexes and Their...

In the present study, density functional theory (DFT) calculation was applied to Vaska's complexes of formula trans-[Ir^IX(CO)(PPh₃)₂] and their oxidative adducts with small molecules (YZ) including H₂, i.e., trans-[Ir^IIIClYZ(CO)(PPh₃)₂], to successfully correlate the electronic states of the complexes with the corresponding ¹⁹³Ir Mössbauer spectroscopic parameters. After confirming the reproducibility of the DFT methods for elucidating the equilibrium structures and ¹⁹³Ir Mössbauer isomer shifts of the octahedral Ir complexes, the isomer shifts and quadrupole splitting values of Vaska's complexes and their oxidative adducts were calculated. A bond critical point analysis revealed that the tendency in the isomer shifts was correlated with the strength of the covalent interaction in the coordination bonds. In an electric field gradient (EFG) analysis of the oxidative adducts, the sign of the principal axis was found to be positive for the complex with YZ = Cl₂ and negative for the complex with YZ = H₂. This reversal of the sign of the EFG principal axis was caused by the difference in the electron density distribution for the coordination bonds between Ir and YZ, according to a density of states analysis.