Angewandte Chemie - International Edition
Angewandte Chemie - International Edition
4 years ago

Reduction of a CeIII Siloxide Complex Affords a Tetradecker Arene-bridged CeII Sandwich

Marinella Mazzanti, Rory Kelly, Rosario Scopelliti, Laurent Maron
Organometallic multiple-decker sandwich complexes containing f-elements remain rare in spite of their attractive magnetic and electronic properties. The reduction of the CeIII siloxide complex, [KCeL4] (1; L = OSi(OtBu)3) with excess potassium in a THF/toluene mixture affords a rare tetradecker arene-bridged complex [K(2.2.2-crypt)]2[{(KL3Ce)(µ-η6:η6-C7H8)}2Ce] (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 data and DFT studies indicate the presence of CeII ions involved in δ bonding between the Ce cations and toluene dianions. Complex 3 is a rare lanthanide multidecker complex and the first containing non-classical divalent lanthanide ions. Moreover, oxidation of 1 by AgOTf (OTf = O3SCF3) yielded the CeIV complex, [CeL4] (2), showing that siloxide ligands can stabilize Ce in three oxidation states.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201709769

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