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Issue 12, 2015
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Control of cerium oxidation state through metal complex secondary structures

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Abstract

A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.

Graphical abstract: Control of cerium oxidation state through metal complex secondary structures

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Publication details

The article was received on 18 Jul 2015, accepted on 10 Aug 2015 and first published on 11 Aug 2015


Article type: Edge Article
DOI: 10.1039/C5SC02607E
Citation: Chem. Sci., 2015,6, 6925-6934
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    Control of cerium oxidation state through metal complex secondary structures

    J. R. Levin, W. L. Dorfner, P. J. Carroll and E. J. Schelter, Chem. Sci., 2015, 6, 6925
    DOI: 10.1039/C5SC02607E

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