New thiocyanato and azido adducts of the redox-active Fe(η5- C5Me5)(η2-dppe) center: Synthesis and study of the Fe(II) and Fe(III) complexes

Floriane Malvolti, Alexander Trujillo, Olivier Cador, Frédéric Gendron, Karine Costuas, Jean Franois Halet, Arnaud Bondon, Loic Toupet, Yann Molard, Stéphane Cordier, Frédéric Paul

Resultado de la investigación: Article

3 Citas (Scopus)

Resumen

The new thiocyanato- (5) and azido- (6) complexes were synthesized and studied under their Fe(II) and Fe(III) redox states. For the first time among the various [Fe(η5-C5Me5) (η2-dppe)]-based cationic radicals studied so far, the magnitude and spatial orientation of the g-tensor diagonal values were experimentally determined for 5[PF6]. These data are in good agreement with those issued from a DFT modelization. The changes experienced by the electronic structure of the Fe(II) complexes subsequent to oxidation are reminiscent of these previously observed for the known arylalkynyl analogues, albeit some differences can be pointed out. Thus, the differences observed in the 1H NMR spectra of 5[PF6] and 6[PF6] are attributed to a slower electronic spin relaxation and to the differently oriented magnetic anisotropy. The sizeable spin density evidenced by DFT on the terminal atom of the ligands of the Fe(III) complexes renders these new paramagnetic metallo-ligands quite appealing for accessing larger polynuclear molecular assemblies with magnetically interacting centers.

Idioma originalEnglish
Páginas (desde-hasta)288-301
Número de páginas14
PublicaciónInorganica Chimica Acta
Volumen374
N.º1
DOI
EstadoPublished - 1 ago 2011

Huella dactilar

Discrete Fourier transforms
adducts
Ligands
ligands
Magnetic anisotropy
synthesis
assemblies
Electronic structure
Tensors
Nuclear magnetic resonance
tensors
analogs
electronic structure
Atoms
Oxidation
nuclear magnetic resonance
oxidation
anisotropy
electronics
atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Citar esto

Malvolti, Floriane ; Trujillo, Alexander ; Cador, Olivier ; Gendron, Frédéric ; Costuas, Karine ; Halet, Jean Franois ; Bondon, Arnaud ; Toupet, Loic ; Molard, Yann ; Cordier, Stéphane ; Paul, Frédéric. / New thiocyanato and azido adducts of the redox-active Fe(η5- C5Me5)(η2-dppe) center : Synthesis and study of the Fe(II) and Fe(III) complexes. En: Inorganica Chimica Acta. 2011 ; Vol. 374, N.º 1. pp. 288-301.
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title = "New thiocyanato and azido adducts of the redox-active Fe(η5- C5Me5)(η2-dppe) center: Synthesis and study of the Fe(II) and Fe(III) complexes",
abstract = "The new thiocyanato- (5) and azido- (6) complexes were synthesized and studied under their Fe(II) and Fe(III) redox states. For the first time among the various [Fe(η5-C5Me5) (η2-dppe)]-based cationic radicals studied so far, the magnitude and spatial orientation of the g-tensor diagonal values were experimentally determined for 5[PF6]. These data are in good agreement with those issued from a DFT modelization. The changes experienced by the electronic structure of the Fe(II) complexes subsequent to oxidation are reminiscent of these previously observed for the known arylalkynyl analogues, albeit some differences can be pointed out. Thus, the differences observed in the 1H NMR spectra of 5[PF6] and 6[PF6] are attributed to a slower electronic spin relaxation and to the differently oriented magnetic anisotropy. The sizeable spin density evidenced by DFT on the terminal atom of the ligands of the Fe(III) complexes renders these new paramagnetic metallo-ligands quite appealing for accessing larger polynuclear molecular assemblies with magnetically interacting centers.",
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author = "Floriane Malvolti and Alexander Trujillo and Olivier Cador and Fr{\'e}d{\'e}ric Gendron and Karine Costuas and Halet, {Jean Franois} and Arnaud Bondon and Loic Toupet and Yann Molard and St{\'e}phane Cordier and Fr{\'e}d{\'e}ric Paul",
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Malvolti, F, Trujillo, A, Cador, O, Gendron, F, Costuas, K, Halet, JF, Bondon, A, Toupet, L, Molard, Y, Cordier, S & Paul, F 2011, 'New thiocyanato and azido adducts of the redox-active Fe(η5- C5Me5)(η2-dppe) center: Synthesis and study of the Fe(II) and Fe(III) complexes', Inorganica Chimica Acta, vol. 374, n.º 1, pp. 288-301. https://doi.org/10.1016/j.ica.2011.03.002

New thiocyanato and azido adducts of the redox-active Fe(η5- C5Me5)(η2-dppe) center : Synthesis and study of the Fe(II) and Fe(III) complexes. / Malvolti, Floriane; Trujillo, Alexander; Cador, Olivier; Gendron, Frédéric; Costuas, Karine; Halet, Jean Franois; Bondon, Arnaud; Toupet, Loic; Molard, Yann; Cordier, Stéphane; Paul, Frédéric.

En: Inorganica Chimica Acta, Vol. 374, N.º 1, 01.08.2011, p. 288-301.

Resultado de la investigación: Article

TY - JOUR

T1 - New thiocyanato and azido adducts of the redox-active Fe(η5- C5Me5)(η2-dppe) center

T2 - Synthesis and study of the Fe(II) and Fe(III) complexes

AU - Malvolti, Floriane

AU - Trujillo, Alexander

AU - Cador, Olivier

AU - Gendron, Frédéric

AU - Costuas, Karine

AU - Halet, Jean Franois

AU - Bondon, Arnaud

AU - Toupet, Loic

AU - Molard, Yann

AU - Cordier, Stéphane

AU - Paul, Frédéric

PY - 2011/8/1

Y1 - 2011/8/1

N2 - The new thiocyanato- (5) and azido- (6) complexes were synthesized and studied under their Fe(II) and Fe(III) redox states. For the first time among the various [Fe(η5-C5Me5) (η2-dppe)]-based cationic radicals studied so far, the magnitude and spatial orientation of the g-tensor diagonal values were experimentally determined for 5[PF6]. These data are in good agreement with those issued from a DFT modelization. The changes experienced by the electronic structure of the Fe(II) complexes subsequent to oxidation are reminiscent of these previously observed for the known arylalkynyl analogues, albeit some differences can be pointed out. Thus, the differences observed in the 1H NMR spectra of 5[PF6] and 6[PF6] are attributed to a slower electronic spin relaxation and to the differently oriented magnetic anisotropy. The sizeable spin density evidenced by DFT on the terminal atom of the ligands of the Fe(III) complexes renders these new paramagnetic metallo-ligands quite appealing for accessing larger polynuclear molecular assemblies with magnetically interacting centers.

AB - The new thiocyanato- (5) and azido- (6) complexes were synthesized and studied under their Fe(II) and Fe(III) redox states. For the first time among the various [Fe(η5-C5Me5) (η2-dppe)]-based cationic radicals studied so far, the magnitude and spatial orientation of the g-tensor diagonal values were experimentally determined for 5[PF6]. These data are in good agreement with those issued from a DFT modelization. The changes experienced by the electronic structure of the Fe(II) complexes subsequent to oxidation are reminiscent of these previously observed for the known arylalkynyl analogues, albeit some differences can be pointed out. Thus, the differences observed in the 1H NMR spectra of 5[PF6] and 6[PF6] are attributed to a slower electronic spin relaxation and to the differently oriented magnetic anisotropy. The sizeable spin density evidenced by DFT on the terminal atom of the ligands of the Fe(III) complexes renders these new paramagnetic metallo-ligands quite appealing for accessing larger polynuclear molecular assemblies with magnetically interacting centers.

KW - Azido complex

KW - ESR

KW - Magnetic anisotropy

KW - Organometallics

KW - Spin delocalization

KW - Thiocyanato complex

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U2 - 10.1016/j.ica.2011.03.002

DO - 10.1016/j.ica.2011.03.002

M3 - Article

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JO - Inorganica Chimica Acta

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