Half-Sandwich Cerium and Lanthanum Dialkyl Complexes: Synthesis, Structure, and Reactivity Studies
Kang Zhu1, Tao Gao1, Song Liu2
1Key Laboratory of Applied Chemistry of Chongqing Municipality, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Abstract:
Cerium and lanthanum dialkyl complexes [η5-1,2,4-(Me3C)3C5H2]Ln(CH2C6H4-o-NMe2)2 (Ln = Ce 1 and La 2), supported by a tri-tert-butylcyclopentadienyl ligand, have been successfully synthesized. Studies demonstrate that these complexes possess diverse reactivity toward various small molecules. For example, the reaction of complexes 1 and 2 with diphenyl dichalcogenides PhEEPh (E = S, Se) results in the formation of lanthanide thiolates [(η5-1,2,4-(Me3C)3C5H2)Ln(SPh)(μ-SPh)]2 (Ln = Ce 3 and La 4) and selenolates [(η5-1,2,4-(Me3C)3C5H2)Ln(SePh)(μ-SePh)]2 (Ln = Ce 5 and La 6), concomitantly releasing PhE(CH2C6H4-o-NMe2). Furthermore, complexes 1 and 2, upon reaction with dibenzyl disulfide, yield tetranuclear rare-earth metallomacrocyclic compounds {[(η5-1,2,4-(Me3C)3C5H2)Ln(μ-SCH2C6H5)]2(μ-η3:η3-SCHC6H5)}2 (Ln = Ce 7 and La 8). This reaction may involve a process of σ-bond metathesis and C-H activation. While the reaction of 1 and 2 with dibenzyl diselenide in the presence of LiCH2C6H4-o-NMe2 leads to the formation of lanthanide-lithium selenido clusters [(η5-1,2,4-(Me3C)3C5H2)La(μ-SeCH2C6H5)]3(μ3-Se)[μ3-SeLi(THF)3] (Ln = Ce 9 and La 10). Meanwhile, lanthanide selenido clusters [(η5-1,2,4-(Me3C)3C5H2)La(μ-SeCH2C6H4-o-NMe2)]4(μ3-Se)2 (Ln = Ce 11 and La 12) can be obtained by treating 1 and 2 with elemental selenium in a 1:2 molar ratio. Additionally, the treatment of 1 and 2 with benzoxazole generates ring-opening/C-C coupling/C-N coupling products {(η5-1,2,4-(Me3C)3C5H2)La[μ-OC6H4-o-N═CHN(CH(CH2C6H4-o-NMe2)2C6H4-o-O]}2 (Ln = Ce 13 and La 14). All new compounds were characterized by various spectroscopic methods, and their solid-state structures were confirmed by single-crystal X-ray diffraction analyses.
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