http://dx.doi.org/10.1002/ejic.201402772">
 

Document Type

Journal Article

Department/Unit

Department of Chemistry

Title

Oxidation of alkylbenzenes with cerium complexes containing a tripodal oxygen ligand

Language

English

Abstract

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.The treatment of [Ce(LOEt)2(NO3)2] (LOEt- = [Co(η5-C5H5){P(O)(OEt)2}3]-) with KMnO4 in water afforded a diamagnetic purple solid 1, which is tentatively formulated as a CeIV permanganate complex, "[Ce(LOEt)2(MnO4)2]". The ZrIV analogue, [Zr(LOEt)2(MnO4)2] (2), has been prepared similarly from [Zr(LOEt)2(NO3)2] and KMnO4. The recrystallization of 1 from CH2Cl2/hexanes at -18 C led to the isolation of dinuclear [(CeLOEt)2(μ-LOEt′)2][MnO4]2 (3), which contains the dianionic tripodal ligand [LOEt′]2- ([(η5-C5H5)Co{P(O)(OEt)2}2{P(O)2(OEt)}]2-). The reactions of 1 with K[ReO4] and [NH4][OsO3N] afforded the heterodimetallic complexes [Ce(LOEt)2(ReO4)2] (4) and [Ce(LOEt)2(NOsO3)2] (5), respectively. The crystal structures of 3 and 5 have been determined. Freshly prepared 1 can oxidize alkylbenzenes such as toluene, ethylbenzene, and cumene at room temperature to give the corresponding ketone and/or alcohol products. Ce-LOEt complexes are efficient promoters of the aerobic oxidation of alkylbenzenes by a radical mechanism. For example, cumene in the presence of [Ce(LOEt)2(H2O)2]Cl (1 mM) in air at 100 C for 10 h afforded a ca. 6:1 mixture of 2-phenyl-2-propanol and acetophenone with a total turnover number of 6810.

Keywords

Alkylbenzenes, Cerium, Heterometallic complexes, O ligands, Oxidation

Publication Date

2014

Source Publication Title

European Journal of Inorganic Chemistry

Volume

2014

Issue

35

Start Page

6097

End Page

6103

Publisher

Wiley-VCH Verlag

ISSN (print)

14341948

ISSN (electronic)

10990682

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