Abstract
Europium and ytterbium complexes [(dpp-Bian)Ln(dme)2] (Ln=Eu (1), Yb(2), dme=1,2-dimethoxyethane) with redox-active dianionic 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene ligand (dpp-Bian) have been tested in the reactions with nitrous oxide and sulfur. The reactions performed in 1:1M ratio afford quantitatively neutral dpp-Bian, while the use of a half equivalent of oxidants leads to the europium complex with two radical-anionic dpp-Bian ligands [(dpp-Bian)2Eu(dme)] (3) and the known ytterbium ionic compound [(dpp-Bian)2Yb]−[(dpp-Bian)Yb(dme)2]+ (4). The same products have been produced by the treatment of 1 and 2 with dpp-Bian. The oxidation of 1 and 2 with either sulfur dioxide or sulfur diimide (Me3SiN=)2S proceeds with the total release of the neutral dpp-Bian. DFT calculations performed for 1 and 2 show pure ligand nature of the frontier molecular orbitals in both cases.
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