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Issue 38, 2016
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Accessing relatively electron poor cerium(IV) hydrazido complexes by lithium cation promoted ligand reduction

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A series of substituted N,N′-diarylhydrazines (ArNHNHAr), Ar = 3,5-(CH3)-C6H3; -Ph; 4-Cl-C6H4; 3,5-Cl-C6H3; 3,5-(CF3)-C6H3, were reacted with Ce(III)[N(SiMe3)2]3 and lithiated bases to explore the use of Ce(III) as a reductant and to evaluate the impact of the ligand substitution on the electronic structure at the cerium metal centre of the resulting complexes. The N,N′-diarylhydrazido ligands were coordinated by the Li+ cation and then reduced by a Ce(III) cation to form Li4(Et2O)4[CeIV(ArNNAr)4] complexes in all cases. Stabilization of the resulting Ce(IV) product depended on the substituents on the N,N′-diarylhydrazido ligands. Isolable cerium products formed only with electron withdrawing substituents on the N,N′-diarylhydrazido rings, whereas electron donating substituents resulted in intractable mixtures of Ce(III) products and N,N′-bis(aryl)diazenes (ArN[double bond, length as m-dash]NAr). The presence of electron withdrawing substituents at the N,N′-diarylhydrazido ligands formed relatively electron poor Ce(IV) complexes, which were probed by UV-Vis spectroscopy, cyclic voltammetry, and DFT calculations. The Lewis acid promoted reduction of hydrazobenzene derivatives by Ce(III) was thus demonstrated to be a successful method to access electron poor cerium(IV) complexes.

Graphical abstract: Accessing relatively electron poor cerium(iv) hydrazido complexes by lithium cation promoted ligand reduction

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Publication details

The article was received on 08 Aug 2016, accepted on 24 Aug 2016 and first published on 25 Aug 2016

Article type: Paper
DOI: 10.1039/C6DT03154D
Citation: Dalton Trans., 2016,45, 15249-15258
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    Accessing relatively electron poor cerium(IV) hydrazido complexes by lithium cation promoted ligand reduction

    J. R. Levin, T. Cheisson, P. J. Carroll and E. J. Schelter, Dalton Trans., 2016, 45, 15249
    DOI: 10.1039/C6DT03154D

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