Archivio istituzionale della ricerca dell'Università degli Studi di Palermo
IRIS è il sistema di gestione integrata dei dati della ricerca (persone, pubblicazioni, progetti, attività) adottato dall’Università di Palermo, e ha lo scopo di raccogliere, conservare, documentare, e diffondere ad accesso aperto le informazioni relative alla produzione scientifica degli autori afferenti all’Ateneo.
EnglishThe unoccupied electronic structures of three closed-shell, highly popular organoiron complexes ([Fe(CO)5], [(η5-C5H5)Fe(CO)(μ-CO)]2, and [(η5-C5H5)2Fe]; 0, I, and II, respectively) have been investigated both experimentally and theoretically by combining original gas-phase X-ray absorption spectroscopy (XAS) outcomes recorded at the C and O K-edge with results of scalar relativistic time-dependent density functional calculations carried out within the zeroth order regular approximation. Experimental evidence herein discussed complement the Fe L2,3-edges XAS ones we recently recorded, modeled, and assigned for the same complexes (Carlotto et al. Inorg. Chem. 2019, 58, 5844). The first-principle simulation of the C and O K-edge features allowed us to univocally identify the electronic states associated to the ligand-to-metal charge transfer (LMCT) transitions both in I and in II. At variance to that, LMCT transitions with sizable oscillator strengths do not play any role in determining neither the C nor the O K-edge spectral pattern of 0. The higher IC-acceptor capability of the CO ligand, regardless of its terminal or bridging coordination, with respect to [(η5-C5H5)]- is herein ultimately confirmed.
Carlotto S., Finetti P., De Simone M., Coreno M., Casella G., Sambi M., et al. (2019). Comparative Experimental and Theoretical Study of the C and O K-Edge X-ray Absorption Spectroscopy in Three Highly Popular, Low Spin Organoiron Complexes: [Fe(CO)5], [(η5-C5H5)Fe(CO)(μ-CO)]2, and [(η5-C5H5)2Fe]. INORGANIC CHEMISTRY, 58(24), 16411-16423.
| Data di pubblicazione: | 2019 | |
| Titolo: | Comparative Experimental and Theoretical Study of the C and O K-Edge X-ray Absorption Spectroscopy in Three Highly Popular, Low Spin Organoiron Complexes: [Fe(CO)5], [(η5-C5H5)Fe(CO)(μ-CO)]2, and [(η5-C5H5)2Fe] | |
| Autori: | ||
| Citazione: | Carlotto S., Finetti P., De Simone M., Coreno M., Casella G., Sambi M., et al. (2019). Comparative Experimental and Theoretical Study of the C and O K-Edge X-ray Absorption Spectroscopy in Three Highly Popular, Low Spin Organoiron Complexes: [Fe(CO)5], [(η5-C5H5)Fe(CO)(μ-CO)]2, and [(η5-C5H5)2Fe]. INORGANIC CHEMISTRY, 58(24), 16411-16423. | |
| Rivista: | ||
| Digital Object Identifier (DOI): | http://dx.doi.org/10.1021/acs.inorgchem.9b02107 | |
| Abstract: | The unoccupied electronic structures of three closed-shell, highly popular organoiron complexes ([Fe(CO)5], [(η5-C5H5)Fe(CO)(μ-CO)]2, and [(η5-C5H5)2Fe]; 0, I, and II, respectively) have been investigated both experimentally and theoretically by combining original gas-phase X-ray absorption spectroscopy (XAS) outcomes recorded at the C and O K-edge with results of scalar relativistic time-dependent density functional calculations carried out within the zeroth order regular approximation. Experimental evidence herein discussed complement the Fe L2,3-edges XAS ones we recently recorded, modeled, and assigned for the same complexes (Carlotto et al. Inorg. Chem. 2019, 58, 5844). The first-principle simulation of the C and O K-edge features allowed us to univocally identify the electronic states associated to the ligand-to-metal charge transfer (LMCT) transitions both in I and in II. At variance to that, LMCT transitions with sizable oscillator strengths do not play any role in determining neither the C nor the O K-edge spectral pattern of 0. The higher IC-acceptor capability of the CO ligand, regardless of its terminal or bridging coordination, with respect to [(η5-C5H5)]- is herein ultimately confirmed. | |
| URL: | http://pubs.acs.org/journal/inocaj | |
| Appare nelle tipologie: | 1.01 Articolo in rivista |
File in questo prodotto:
| File | Descrizione | Tipologia | Licenza | |
|---|---|---|---|---|
| IC_2019_2.pdf | Articolo | Versione Editoriale | Administrator Richiedi una copia |
http://hdl.handle.net/10447/399422
Copyright © 2021