Abstract
The electronic structure perturbations caused by cyclopentadienyl substitutions in the series of complexes (η5-C5H5)2Ru, (η5-C5Me5)(η5-C5H5)Ru, (η5-C5Me5)2Ru, (η5-C5Me5)(η5-C5Cl5)Ru, and (η5-C5Me5)(η5-C5F5)Ru are measured by gas-phase photoelectron spectroscopy. The shifts of the valence metal- and cyclopentadienyl-based ionizations give an indication of the overall electronic effects of methyl and halogen substitutions on the cyclopentadienyl rings. The halogen substituent interaction is an admixture of inductive σ-electron-withdrawing and filled−filled π-electron-overlap effects, which act in opposite directions. The π-overlap interaction is relatively weak in the case of chlorine substitution for hydrogen, and the combined σ and π interactions give rise to an overall withdrawal of electron density from the metal center and increase in the metal d-based ionization energies. Fluorine substituents on cyclopentadienyl make the ring only slightly more electron withdrawing than η5-C5Cl5, despite the much gre...
Published Version
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