Articles producció científica> Química Física i Inorgànica

Role of the imide axial ligand in the spin and oxidation state of Mn corrole and corrolazine complexes 

  • Identification data

    Identifier: PC:3124
    Authors:
    Caballol, R.Alcover-Fortuny, G.Pierloot, K.De Graaf, C.
    Abstract:
    Filiació URV: SI
  • Others:

    Author, as appears in the article.: Caballol, R. ; Alcover-Fortuny, G. ; Pierloot, K. ; De Graaf, C.
    Department: Química Física i Inorgànica
    URV's Author/s: CABALLOL LORENZO, ROSA; Alcover-Fortuny, G. ; Pierloot, K. ; DE GRAAF , CORNELIS
    Keywords: DFT calculations electronic structure
    Abstract: Electronic structure calculations have been performed on four dierent Mn corrole and corrolazine complexes to clarify the role of the imide axial ligand on the relative stability of the dierent spin states and the stabilization of the high valent Mn ion in these complexes. Multicongurational perturbation theory energy calculations on the DFT optimized geometries shows that all complexes have a singlet ground state except the complex with the strongest electron with- drawal axial ligand, which is found to have a triplet ground state. The analysis of the sigma and pi interaction between metal and imide ligand shows that this spin crossover is caused by a subtle interplay of geometrical factors (Mn-N distance and coordination angle) and the electron withdrawal character of the imide. The analysis of the multicongurational wave functions reveals that the formally MnV ion is stabilized by an important electron transfer from both the equatorial cor-role/corrolazine ligand and the axial imide. The macrocycle donates roughly half an electron, being somewhere between the closed-shell trianionic and the dian-ionic radical form. The imide ligand transfers 2.5 electrons to the metal center, resulting in an eective d-electron count close to ve in all complexes.
    Research group: Química Quàntica
    Thematic Areas: Química Química Chemistry
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0020-1669
    Author identifier: 0000-0003-1946-3497; ; ; 0000-0001-8114-6658
    Record's date: 2018-02-28
    Last page: 5280
    Journal volume: 55
    Papper version: info:eu-repo/semantics/submittedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b00194
    Funding program: plan; Excelencia; CTQ2014- 51938-P altres; Grupos Consolidados; 2014SGR199 altres; Red de Química Teórica; XRQTC european; COST Ac- tion ECOSTBio; CM1305
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1021/acs.inorgchem.6b00194
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2016
    First page: 5274
    Publication Type: Article Artículo Article
  • Keywords:

    Estructura electrònica
    Funcional de densitat, Teoria del
    Manganès--Compostos
    DFT calculations
    electronic structure
    Química
    Química
    Chemistry
    0020-1669
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