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]

Girolamo Casella, Silvia Carlotto, Marcello Coreno, Mauro Sambi, Maurizio Casarin, Paola Finetti, Monica De Simone

Risultato della ricerca: Article

1 Citazioni (Scopus)

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.
Lingua originaleEnglish
pagine (da-a)16411-16423
Numero di pagine13
RivistaInorganic Chemistry
Volume58
Stato di pubblicazionePublished - 2019

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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