Reactivity studies on lanthanum and cerium hydrido metallocenes

Yi, Chengkun; Wu, Lei; Chen, Liang; Ren, Wenshan

doi:10.1039/d2dt00996j

Dalton Trans.

2022

DOI: 10.1039/d2dt00996j

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Reactivity studies on lanthanum and cerium hydrido metallocenes

Chengkun Yi

Lei Wu

Liang Chen

et al.

Abstract: The alkyl complexes [5-1,3-(Me3C)2C5H3]2Ln(CH2C6H4-o-NMe2) (Ln = La 1, Ce 2) react with 9-borabicyclo[3.3.1]nonane (9-BBN) in THF to afford the lanthanum boroxide complex [5-1,3-(Me3C)2C5H3]2La(µ-OBC8H14)(THF) (3) and cerium boroxide complex [5-1,3-(Me3C)2C5H3]2Ce(µ-OBC8H14)(THF) (4)....

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Cited by 2 publications

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Half-Sandwich Cerium and Lanthanum Dialkyl Complexes: Synthesis, Structure, and Reactivity Studies

Zhu,

Gao,

Liu

et al. 2024

Inorg. Chem.

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Cerium and lanthanum dialkyl complexes [η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 ]Ln(CH 2 C 6 H 4 -o-NMe 2 ) 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 thiolates5 and La 6), concomitantly releasing PhE(CH 2 C 6 H 4 -o-NMe 2 ). Furthermore, complexes 1 and 2, upon reaction with dibenzyl disulfide, yield tetranuclear rare-earth metallomacrocyclic compounds {[(η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 )Ln(μ-SCH 2 C 6 H 5 )] 2 (μ−η 3 :η 3 -SCHC 6 H 5 )} 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 LiCH 2 C 6 H 4 -o-NMe 2 leads to the formation of lanthanide-lithium selenido clusters [(η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 )La(μ-SeCH 2 C 6 H 5 )] 3 (μ 3 -Se)[μ 3 -SeLi(THF) 3 ] (Ln = Ce 9 and La 10). Meanwhile, lanthanide selenido clusters [(η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 )La(μ-SeCH 2 C 6 H 4 -o-NMe 2 )] 4 (μ 3 -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 {(η 5 -1,2,4-(Me 3 C) 3 C 5 H 2 )La[μ-OC 6 H 4 -o-N�CHN(CH(CH 2 C 6 H 4 -o-NMe 2 ) 2 C 6 H 4 -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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Half-Sandwich Cerium and Lanthanum Dialkyl Complexes: Synthesis, Structure, and Reactivity Studies

Zhu,

Gao,

Liu

et al. 2024

Inorg. Chem.

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Recent progress on the functionalization of white phosphorus in China

Huangfu,

Wang,

Chen

et al. 2024

National Science Review

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Direct synthesis of organophosphorus compounds from white phosphorus represents a significant but challenging subject, especially in the context of ongoing efforts to comprehensively improve phosphorus-derived chemical industry driven by sustainability and safety concerns. China is the world's largest producer of white phosphorus, creating a significant demand for the green transformation of this crucial feedstock. This review provides an overview of advancements in white phosphorus activation by Chinese research teams, organized by the direct construction of P−C/N/O/S/M bonds from white phosphorus. Additionally, we offer some insights into prospective directions for the activation and transformation of white phosphorus in the future. This review paper aims to attract more researchers to engage in this area, stimulating follow-up exploration and fostering enduring advances.

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Reactivity studies on lanthanum and cerium hydrido metallocenes

Cited by 2 publications

References 69 publications

Half-Sandwich Cerium and Lanthanum Dialkyl Complexes: Synthesis, Structure, and Reactivity Studies

Half-Sandwich Cerium and Lanthanum Dialkyl Complexes: Synthesis, Structure, and Reactivity Studies

Recent progress on the functionalization of white phosphorus in China

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