Ligand-field model of photoinduced isomerizations of ruthenium(III) complexes

Abstract

The substitution photostereochemistry of octahedral d1 2345 complexes is analyzed on the example of cis-and trans-disubstituted Ru(III) amines. On the basis of a dissociative mechanism, state correlation diagrams suggest important differences between d5 and d6 photochemistry. The absence of thermally equilibrated excited states in the five-coordinated fragment may be a specific d5 feature.

Flash Photolysis and Chemistry of Transients and Excited States

“…60,61 Although the model was based on the ligand field theory, other applications used the angular overlap model to include geometry changes in a transition state. No doubt, further refinements can be made with more modern computational methods such as DFT.…”