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Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2018

The surprisingly high ligation energy of CO to Ruthenium porphyrins

Résumé

A combined theoretical and experimental approach has been used to investigate the binding energy of a ruthenium metalloporphyrin ligated with CO, ruthenium tetraphenyl porphyrin [Ru II TPP] in the Ru II oxidation degree. Measurements made by VUV ionization with the DESIRS beamline at Synchrotron SOLEIL lead to adiabatic ionization energies of [Ru II TPP] and its complex with CO, [Ru II TPP-CO], to be 6.48±0.03 eV and 6.60±0.03 eV, respectively while the ion dissociation threshold of [Ru II TPP-CO] + is measured at 8.36±0.03 eV. These experimental data are used to derive binding energies of the CO ligand in the neutral and cationic complex (1.88±0.06 eV and 1.76±0.06 eV, respectively) using a Born-Haber cycle. Density Functional Theory calculations, in very satisfactory agreement with the experimental results, help to get insights into the metal-ligand bond. Notably, the high ligation energies can be rationalized in terms of the ruthenium orbital structure, which is singular from that of the iron atom. Thus, beyond indications of a strengthening of the Ru-CO bond from the decrease in the CO vibrational frequency in the complex as compared to the Fe-CO bond, high level calculations are essential to describe accurately the metal ligand (CO) bond and show that the Ru-CO bond energy is strongly affected by the splitting of triplet and singlet spin states in uncomplexed [Ru TPP].
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Dates et versions

hal-01891524 , version 1 (09-10-2018)

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Niloufar Shafizadeh, Séverine Boyé-Péronne, Satchin Soorkia, Barbara Cunha de Miranda, Gustavo Garcia, et al.. The surprisingly high ligation energy of CO to Ruthenium porphyrins. Physical Chemistry Chemical Physics, 2018, 20 (17), pp.11730-11739. ⟨10.1039/C8CP01190G⟩. ⟨hal-01891524⟩
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