Influence of the C5R5 (R=H or Me) ring substituents on the electrochemistry of {Mo2(C5R5)2(μ-SR′) 2} complexes (R′=Me, Ph) and on the reactivity of electrogenerated intermediates with unsaturated substrates - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue New Journal of Chemistry Année : 1997

Influence of the C5R5 (R=H or Me) ring substituents on the electrochemistry of {Mo2(C5R5)2(μ-SR′) 2} complexes (R′=Me, Ph) and on the reactivity of electrogenerated intermediates with unsaturated substrates

Résumé

The effect of the C5R5 ring substituents on the electrochemical behavior of various complexes possessing the {Mo2Cp2′-SR)2} core (Cp′=C5H5 or C5Me5) and on the reactivity of electrogenerated intermediates with unsaturated substrates has been investigated. The increase of the electron density at the metal centers and the increase of the bulkiness of the rings resulting from the C5H5→C5Me5 substitution produce various effects (shift of the redox potentials, ring-dependent geometrical change, stabilization of Mo-NCX bonds (X=Me or O), stabilization of intermediates generated from the reduction of the compounds) depending on the nature of the complex considered. Comparison of the electrochemistry of analogs in the C5H5 and C5Me5 series allows a better understanding of the reduction mechanisms of the complexes with C5H5 rings the C5H5→C5Me5 substitution leads to the stabilization of intermediates whose formation was not detected by CV in the C5H5 series, but could only be inferred from trapping experiments. The C5H5→C5Me5 substitution also results in reactive sites showing a lower selectivity, since the sites with C5Me5 rings still bind electron-withdrawing ligands (CO, CNR), but also ligands with mediocre π-accepting capabilities (MeCN), which are not strongly retained at the metal centers for Cp′=C5H5. © CNRS-Gauthier-Villars.
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hal-02296676 , version 1 (25-09-2019)

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  • HAL Id : hal-02296676 , version 1

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F.Y. Pétillon, S. Poder-Guillou, Philippe P. Schollhammer, J. Talarmin. Influence of the C5R5 (R=H or Me) ring substituents on the electrochemistry of {Mo2(C5R5)2(μ-SR′) 2} complexes (R′=Me, Ph) and on the reactivity of electrogenerated intermediates with unsaturated substrates. New Journal of Chemistry, 1997, 21 (4), pp.477-494. ⟨hal-02296676⟩
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