| Abstract
| - A comparison of the electronic properties and photochemical reactivity efficiencies for a series of rhodiumdicarbonyl complexes with the general formula XRh(CO)2, where X = Cp (η5-C5H5), Cp‘ (η5-C5H4Me), Cp‘ ‘(η5-C5HMe4), Cp* (η5-C5Me5), ind (η5-C9H7), and acac (C5H7O2), has been achieved. The photochemical reactionsof these molecules have been studied under a variety of experimental conditions, where binucleation, intermolecularSi−H and C−H bond activation, and ligand substitution processes occur. Modifications of the unique ligand inthis system enable the photoefficiency of the CO dissociation reaction to be substantially changed. The absolutereaction quantum efficiencies (φcr) are markedly different and strongly wavelength dependent for each of themolecules studied. The values of φcr decrease in the order CpRh(CO)2> Cp‘Rh(CO)2> Cp*Rh(CO)2 ≫(acac)Rh(CO)2> (ind)Rh(CO)2 and vary by over 3 orders of magnitude depending on the complex chosen andthe excitation wavelength employed. The results obtained indicate that the photoefficiencies of these complexesare predominantly determined by radiative and nonradiative decay processes of neighboring excited states andthe electronic and steric properties of the unique ligand.
- A comparison of the electronic absorption spectra and photochemical reactivity efficiencies for a series of rhodium dicarbonyl complexes with the general formula XRh(CO)2, where X = η5-C5H5, η5-C5H4Me, η5-C5HMe4, η5-C5Me5, η5-C9H7, and C5H7O2, is presented. The results obtained indicate that the photoefficiencies of these complexes appear to be predominantly determined by radiative and nonradiative decay processes of neighboring excited states and the electronic and steric properties of the unique ligand.
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