Articles producció científica> Química Física i Inorgànica

When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky

  • Identification data

    Identifier: imarina:9262518
    Handle: https://hdl.handle.net/20.500.11797/imarina9262518
    Authors:
    Laurans MMattera MSalles RK'Bidi LGouzerh PRenaudineau SVolatron FGuillemot GBlanchard SIzzet GSolé-Daura APoblet JMProust A
    Abstract:
    The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA)4[PW9Mo2O39{Sn(C6H4I)}] (TBA = tert-butylammonium) has been prepared by the reaction between [α-PW9Mo2O39]7- and [Cl3Sn(C6H4I)] in dried acetonitrile, in the presence of tetra-n-butylammonium bromide. A further coupling reaction affords the ferrocenyl derivative (TBA)4[PW9Mo2O39{Sn(C6H4)C≡C(C6H4)Fc}]. The POM hybrids have been thoroughly characterized by NMR and IR spectroscopies. Electrochemical analysis confirms their ease of reduction compared to the all-W analogue, albeit with a second reduction process occurring at a lower potential than in the all-Mo species. It is noteworthy that the second reduction is accompanied by an unusual red shift of the electronic absorption spectrum. Whereas there is no doubt that the first reduction deals with Mo, the location of the second electron in the bireduced species, on the second Mo or on W, has thus been the subject of a cross-investigation by spectroelectrochemistry, electron spin resonance, and theoretical calculations. Finally, it came out that the second reduction is also Mo-centered with two unpaired and antiferromagnetically coupled extra electrons.

  • Others:

    Author, as appears in the article.: Laurans M; Mattera M; Salles R; K'Bidi L; Gouzerh P; Renaudineau S; Volatron F; Guillemot G; Blanchard S; Izzet G; Solé-Daura A; Poblet JM; Proust A
    Department: Química Física i Inorgànica
    URV's Author/s: Poblet Rius, Josep Maria / Solé Daura, Albert
    Keywords: Molecular-orbital methods vibrational investigations redox potentials post-functionalization metal-oxide clusters magnetic-properties heteropoly blues electron delocalization charge-separation ab-initio calculation
    Abstract: The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA)4[PW9Mo2O39{Sn(C6H4I)}] (TBA = tert-butylammonium) has been prepared by the reaction between [α-PW9Mo2O39]7- and [Cl3Sn(C6H4I)] in dried acetonitrile, in the presence of tetra-n-butylammonium bromide. A further coupling reaction affords the ferrocenyl derivative (TBA)4[PW9Mo2O39{Sn(C6H4)C≡C(C6H4)Fc}]. The POM hybrids have been thoroughly characterized by NMR and IR spectroscopies. Electrochemical analysis confirms their ease of reduction compared to the all-W analogue, albeit with a second reduction process occurring at a lower potential than in the all-Mo species. It is noteworthy that the second reduction is accompanied by an unusual red shift of the electronic absorption spectrum. Whereas there is no doubt that the first reduction deals with Mo, the location of the second electron in the bireduced species, on the second Mo or on W, has thus been the subject of a cross-investigation by spectroelectrochemistry, electron spin resonance, and theoretical calculations. Finally, it came out that the second reduction is also Mo-centered with two unpaired and antiferromagnetically coupled extra electrons.
    Thematic Areas: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: josepmaria.poblet@urv.cat
    Author identifier: 0000-0002-4533-0623
    Record's date: 2024-09-07
    Papper version: info:eu-repo/semantics/publishedVersion
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Inorganic Chemistry. 61 (20): 7700-7709
    APA: Laurans M; Mattera M; Salles R; K'Bidi L; Gouzerh P; Renaudineau S; Volatron F; Guillemot G; Blanchard S; Izzet G; Solé-Daura A; Poblet JM; Proust A (2022). When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky. Inorganic Chemistry, 61(20), 7700-7709. DOI: 10.1021/acs.inorgchem.2c00866
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2022
    Publication Type: Journal Publications

  • Keywords:

    Chemistry (Miscellaneous),Chemistry, Inorganic & Nuclear,Inorganic Chemistry,Physical and Theoretical Chemistry
    Molecular-orbital methods
    vibrational investigations
    redox potentials
    post-functionalization
    metal-oxide clusters
    magnetic-properties
    heteropoly blues
    electron delocalization
    charge-separation
    ab-initio calculation
    Química
    Physical and theoretical chemistry
    Medicina i
    Materiais
    Interdisciplinar
    Inorganic chemistry
    General medicine
    Farmacia
    Engenharias iii
    Engenharias ii
    Engenharias i
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Chemistry, inorganic & nuclear
    Chemistry (miscellaneous)
    Biotecnología
    Astronomia / física

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