Cerium-quinone redox couples put under scrutiny.

Homoleptic cerous complexes Ce[N(SiMe3)2]3, [Ce{OSi(OtBu)3}3]2 and [Ce{OSiiPr3}3]2 were employed as thermally robust, weakly nucleophilic precursors to assess their reactivity towards 1,4-quinones in non-aqueous solution. The strongly oxidizing quinones 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or tetrachloro-1,4-benzoquinone (Cl4BQ) readily form hydroquinolato-bridged ceric complexes of the composition [(CeIVL3)2(μ2-O2C6R4)]. Less oxidising quinones like 2,5-di-tert-butyl-1,4-benzoquinone (tBu2BQ) tend to engage in redox equilibria with the ceric hydroquinolato-bridged form being stable only in the solid state. Even less oxidising quinones such as tetramethyl-1,4-benzoquinone (Me4BQ) afford cerous semiquinolates of the type [(CeIIIL2(thf)2)(μ2-O2C6Me4)]2. All complexes were characterised by X-ray diffraction, 1H, 13C{1H} and 29Si NMR spectroscopy, DRIFT spectroscopy, UV-Vis spectroscopy and CV measurements. The species putatively formed during the electrochemical reduction of [CeIV{N(SiMe3)2}3]2(μ2-O2C6H4) could be mimicked by chemical reduction with CoIICp2 yielding [(CeIII{N(SiMe3)2}3)2(μ2-O2C6H4)][CoIIICp2]2.