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Issue 8, 2012
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Multielectron redox chemistry of lanthanide Schiff-base complexes

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Abstract

Multielectron redox chemistry, which is essential in metal catalysed chemical transformations, is not easily accessible in lanthanide complexes. Here we explored the reductive chemistry of lanthanide complexes with tetradentate Schiff bases acting as redox-active ligands with the objective of identifying new pathways to lanthanide multielectron redox transfer. The chemical reduction with alkali metals of heteroleptic [Nd(salophen)X] (salophen = N,N′-bis(salicylidene)phenylenediamine, X = I, OTf) and of a series of homoleptic K[Ln(Rsalophen)2] complexes of trivalent lanthanides has resulted respectively in the synthesis of the new dinuclear Nd(III) complex K2[Nd2(cyclo-salophen)(THF)2] and in the synthesis of a series of mononuclear lanthanide(III) complexes of general formula K3[Ln(bis-Rsalophen)] (R = H, Me, tBu). Ligand reduction and C–C bond formation are supported by X-ray crystal structures. Proton NMR studies demonstrate that the K2[Nd2(cyclo-salophen)(py)2] complex can transfer four electrons in the reaction with oxidizing agents such as AgOTf through the breaking of the two C–C bonds. Moreover the electrochemistry and reactivity of the mononuclear complexes K3[Ln(bis-Rsalophen)] show that they can act as formal two electron reductants and that their oxidation potential can be tuned by changing the substituents on the ligand. These results illustrate that Schiff bases provide a new way to introduce multielectron redox events at lanthanide centers and a new route to highly reactive mono- and polynuclear complexes of lanthanides.

Graphical abstract: Multielectron redox chemistry of lanthanide Schiff-base complexes

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Publication details

The article was received on 18 Apr 2012, accepted on 26 May 2012 and first published on 30 May 2012


Article type: Edge Article
DOI: 10.1039/C2SC20476B
Citation: Chem. Sci., 2012,3, 2433-2448
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    Multielectron redox chemistry of lanthanide Schiff-base complexes

    C. Camp, V. Guidal, B. Biswas, J. Pécaut, L. Dubois and M. Mazzanti, Chem. Sci., 2012, 3, 2433
    DOI: 10.1039/C2SC20476B

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