Abstract

Reactions between LnCl3, AlCl3 and a crown ether (18-crown-6 and dibenzo18-crown-6) in MeCN have led to the isolation of four new lanthanoid halide crown ether complexes, [PrCl(μ-Cl)(18-crown-6)]2[AlCl4]2·2MeCN (1), [YbCl2(18-crown-6)][AlCl4]·MeCN (2), and [LnCl(μ-Cl)(dibenzo18-crown-6)}2][AlCl4]2·6.5MeCN (Ln = La, 3, Pr, 4). 1 was also obtained by unexpected halide transfer on addition of 18-crown-6 (18C6) to MeCN solutions of [Pr(MeCN)9][AlCl4]3. Complexes 1, 3 and 4 have dinuclear chloride-bridged nine-coordinate cations, and 2 has an eight coordinate mononuclear cation.

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