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Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2019, 58, 24, 16411-16423
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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]

  • Silvia Carlotto*
    Silvia Carlotto
    Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Francesco Marzolo 1, 35131 Padova, Italy
    *E-mail: [email protected] (S.C.).
    More by Silvia Carlotto
    Orcidhttp://orcid.org/0000-0003-0043-3538
  • , 
  • Paola Finetti
    Paola Finetti
    Dipartimento di Scienze e Metodi dell’Ingegneria, Università di Modena, Via Università 4, 41121 Modena, Italy
    More by Paola Finetti
  • , 
  • Monica de Simone
    Monica de Simone
    CNR−IOM, Strada Statale 14 Basovizza, 34149 Trieste, Italy
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  • , 
  • Marcello Coreno
    Marcello Coreno
    CNR−ISM, Strada Statale 14 Basovizza, 34149 Trieste, Italy
    More by Marcello Coreno
    Orcidhttp://orcid.org/0000-0003-4376-808X
  • , 
  • Girolamo Casella
    Girolamo Casella
    Dipartimento di Scienze della Terra e del Mare, Università degli Studi di Palermo, Via Archirafi 22, 90123 Palermo, Italy
    More by Girolamo Casella
    Orcidhttp://orcid.org/0000-0002-8471-0848
  • , 
  • Mauro Sambi
    Mauro Sambi
    Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Francesco Marzolo 1, 35131 Padova, Italy
    Consorzio INSTM, Unità di Ricerca di Padova, Via Marzolo 1, 35131 Padova, Italy
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    Orcidhttp://orcid.org/0000-0002-7105-4001
  • , and 
  • Maurizio Casarin*
    Maurizio Casarin
    Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Francesco Marzolo 1, 35131 Padova, Italy
    CNR−ICMATE, Via Francesco Marzolo 1, 35131 Padova, Italy
    *E-mail: [email protected] (M.C.).
    More by Maurizio Casarin
Cite this: Inorg. Chem. 2019, 58, 24, 16411–16423
Publication Date (Web):November 22, 2019
https://doi.org/10.1021/acs.inorgchem.9b02107
Copyright © 2019 American Chemical Society
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    Abstract

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    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 π-acceptor capability of the CO ligand, regardless of its terminal or bridging coordination, with respect to [(η5-C5H5)]− is herein ultimately confirmed.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b02107.

    • (Tables S1–S4) Energy ordered C and O 1s-based SALCs of 0, t-I, s-II, and e-II; (Table S5) symmetry constraints on s-II and e-II σ → π* transitions; (Tables S6–S11) SR ZORA TD-DFT compositions, oscillator strength (f), and excitation energy (EE) values of transitions associated with electronic states generating the C and O K-edge spectral features of 0, t-I, s-II, and e-II; (Figure S1) SR ZORA TD-DFT C 1s excitation spectra of t-I modeled with diverse XC functionals; (Figure S2) SR ZORA TD-DFT C 1s excitation spectra of s-II modeled with diverse XC functionals; and (Figure S3) SR ZORA TD-DFT C and O 1s excitation spectra of t-I and c-I (PDF)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 5 publications.

    1. Girolamo Casella, Silvia Carlotto, Leonardo Belpassi, Mauro Sambi, Maurizio Casarin. Donation and back-donation in cis- and trans-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2 tautomers: Which relative is more generous? An ETS-NOCV bond analysis. Inorganica Chimica Acta 2022, 536 , 120897. https://doi.org/10.1016/j.ica.2022.120897
    2. Silvia Carlotto, Girolamo Casella, Mauro Sambi, Maurizio Casarin. cis -[(η 5 -C 5 H 5 )Fe(η 1 -CO)(μ-CO)] 2 , the poor relative between cis and trans tautomers. A theoretical study of the gas-phase Fe L 3 -edge and C and O K-edge XAS of trans -/ cis -[(η 5 -C 5 H 5 )Fe(η 1 -CO)(μ-CO)] 2. Physical Chemistry Chemical Physics 2021, 23 (43) , 24661-24668. https://doi.org/10.1039/D1CP04105C
    3. Gerui Pei, Cong-Cong Shu, Mengyang Li, Zhong-Ming Sun, Tao Yang. Electronic structures and properties of dianionic pentacarbonyls [TM(CO) 5 ] 2− (TM = Cr, Mo, W). Physical Chemistry Chemical Physics 2021, 23 (34) , 18640-18646. https://doi.org/10.1039/D1CP01592C
    4. Silvia Carlotto, Mauro Sambi, Francesco Sedona, Andrea Vittadini, Maurizio Casarin. A Theoretical Study of the Occupied and Unoccupied Electronic Structure of High- and Intermediate-Spin Transition Metal Phthalocyaninato (Pc) Complexes: VPc, CrPc, MnPc, and FePc. Nanomaterials 2021, 11 (1) , 54. https://doi.org/10.3390/nano11010054
    5. Silvia Carlotto, Elaheh Mohebbi, Francesco Sedona, Matteo Lo Cicero, Luciano Colazzo, Carlo Mariani, Maria Grazia Betti, Mauro Sambi, Maurizio Casarin. An experimental and theoretical study of metallorganic coordination networks of tetrahydroxyquinone on Cu(111). New Journal of Chemistry 2019, 43 (48) , 19186-19192. https://doi.org/10.1039/C9NJ04884G
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