Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple-Decker Arene-Bridged Cerium(II) Sandwich - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Angewandte Chemie International Edition Year : 2017

Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple-Decker Arene-Bridged Cerium(II) Sandwich

Abstract

Organometallic multi-decker sandwich complexes containing f-elements remain rare, despite their attractive magnetic and electronic properties. The reduction of the Ce-III siloxide complex, [KCeL4] (1; L = OSi(OtBu)(3)), with excess potassium in a THF/toluene mixture afforded a quadruple-decker arene-bridged complex, [K(2.2.2-crypt)](2)[\(KL3Ce)(mu-eta(6):eta(6)-C7H8)\(2)Ce] (3). The structure of 3 features a [Ce(C7H8)(2)] sandwich capped by [KL3Ce] moieties with a linear arrangement of the Ce ions. Structural parameters, UV/Vis/NIR data, and DFT studies indicate the presence of Ce-II ions involved in delta bonding between the Ce cations and toluene dianions. Complex 3 is a rare lanthanide multi-decker complex and the first containing non-classical divalent lanthanide ions. Moreover, oxidation of 1 by AgOTf (OTf = O3SCF3) yielded the Ce-IV complex, [CeL4] (2), showing that siloxide ligands can stabilize Ce in three oxidation states.
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Dates and versions

hal-01961153 , version 1 (19-12-2018)

Identifiers

  • HAL Id : hal-01961153 , version 1

Cite

Rory P. Kelly, Laurent Maron, Rosario Scopelliti, Marinella Mazzanti. Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple-Decker Arene-Bridged Cerium(II) Sandwich. Angewandte Chemie International Edition, 2017, 56 (49), pp.15663--15666. ⟨hal-01961153⟩
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