A density functional theory study on ligand additive effects on redox potentials.

摘要: Adiabatic energy differences ΔEadiabatic are computed at density functional theory (DFT) level for the oxidation half reaction of [M(CO)nL6−n] complexes (M = Ru2+/3+, Os2+/3+, Tc2+/3+; L CN−, Cl−, water, CH3CN, N2 and CO). Linear trends in with respect to substitution number n(CO) support hypothesis additive ligand effects on redox potential. The values slope these linear regression curves shown be independent metal type (Ru, Os Tc) can therefore act as a specific parameter. Based parameters, electrochemical series was constructed, which good agreement Pickett's PL, Lever EL(L) CEP parameters. linearity is also reflected structural properties such M–CO bond distances complexes. An decomposition analysis between fragment gave an additional insight into ligand's bonding terms electrostatic orbital contributions.