Issue 43, 2014
From the journal:

Dalton Transactions

Variation of electronic transitions and reduction potentials of cerium(iv) complexes†

Ursula J. Williams,a   David Schneider,b   Walter L. Dorfner,a   Cäcilia Maichle-Mössmer,b   Patrick J. Carroll,a   Reiner Anwander*b  and  Eric J. Schelter*a  

* Corresponding authors

a P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, USA
E-mail: schelter@sas.upenn.edu

b Institute of Inorganic Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, D-72076 Tübingen, Germany
E-mail: reiner.anwander@uni-tuebingen
Fax: (+49) 7071 29 35271

Abstract

The trivalent compound K[Ce[N(SiHMe2)2]4] was synthesized and oxidized, providing a convenient route to the reported cerium(IV) compound Ce[N(SiHMe2)2]4. Protonolysis reactions of Ce[N(SiHMe2)2]4 with tert-butanol, substituted benzyl alcohols, and 2,6-diphenylphenol yielded the neutral tetravalent compounds Ce(OtBu)4(py)2, Ce2(OCH2C6R5)8(thf)2 (R = Me, F), and Ce(Odpp)4 (dpp = 2,6-(C6H5)2-C6H3). Spectroscopic and electrochemical characterization of the monometallic cerium(IV) silylamide, alkoxide, and aryloxide compounds revealed variable ligand-to-metal charge transfer transitions and metal-based reduction potentials. Computational bonding analyses were performed to complement the physical characterization of the complexes.

Graphical abstract: Variation of electronic transitions and reduction potentials of cerium(iv) complexes

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Article information

DOI
https://doi.org/10.1039/C4DT01386G
Article type
Paper
Submitted
09 May 2014
Accepted
28 Jul 2014
First published
29 Jul 2014

Dalton Trans., 2014,43, 16197-16206

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Variation of electronic transitions and reduction potentials of cerium(IV) complexes

U. J. Williams, D. Schneider, W. L. Dorfner, C. Maichle-Mössmer, P. J. Carroll, R. Anwander and E. J. Schelter, Dalton Trans., 2014, 43, 16197 DOI: 10.1039/C4DT01386G

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