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Issue 11, 2018
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Versatile reactivities of rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized β-diketiminato ligand

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Abstract

Herein, rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized β-diketiminato ligand with the formula LRE(CH2SiMe3)2(thf) (RE = Y (1a), Dy (1b), Er (1c), Yb (1d); L = MeC(NDipp)CHC(Me)NCH2CH2NC4H2-2,5-Me2, Dipp = 2,6-iPr2C6H3) were synthesized via the reactions of the β-diketimine HL with the rare-earth metal trialkyl complexes RE(CH2SiMe3)3(thf)2 in high yields. The reactivities of 1 with pyridine derivatives, unsaturated substrates, and elemental sulfur were investigated, and some interesting chemical transformations were observed. Ligand exchange and activation of sp2 and sp3 C–H bonds occurred during the reactions with pyridine derivatives to afford different types of mononuclear rare-earth metal pyridyl complexes, namely, LEr(CH2SiMe3)21-NC5H4) (2c), LRE(η3-CH2-2-NC5H2-4,6-Me2)2 (RE = Y (3a), Er (3c)), and LRE(CH2SiMe3)(η2-(C,N)-2-(2-C6H4NC5H4)) (RE = Er (4c), Yb = (4d)). Similarly, activation of the sp C–H bond occurred during the reaction of phenylacetylene with 1c to produce the dinuclear erbium alkynyl complex [LEr(CH2SiMe3)(μ-C[triple bond, length as m-dash]CPh)]2 (5c). The mixed amidinate-β-diketiminato ytterbium complex LYb[(Dipp)NC(CH2SiMe3)N(Dipp)](CH2SiMe3) (6d) was obtained by the insertion of bis(2,6-diisopropylphenyl)carbodiimide into a Yb-alkyl bond, as well as via the direct alkane elimination of a CH2SiMe3 moiety with bis(2,6-diisopropylphenyl)formamidine to afford the erbium complex LEr(DippNCHNDipp)(CH2SiMe3) (7c). A rare sp2 C–H bond oxidation of the β-diketiminato backbone with elemental sulfur insertion was detected to provide the unprecedented dinuclear rare-earth metal thiolate complexes (LRE)2(μ-SCH2SiMe3)2(μ-SCC(Me)(NDipp)C(Me)NCH2CH2NC4H2Me2-2,5) (RE = Y (8a), Er (8c)) in the reactions of S8 with 1a and 1c, respectively. The molecular structures of the complexes 1–8 were determined by single-crystal X-ray diffraction analyses.

Graphical abstract: Versatile reactivities of rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized β-diketiminato ligand

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Publication details

The article was received on 23 Nov 2017, accepted on 05 Feb 2018 and first published on 06 Feb 2018


Article type: Paper
DOI: 10.1039/C7DT04410K
Citation: Dalton Trans., 2018,47, 3947-3957
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    Versatile reactivities of rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized β-diketiminato ligand

    X. Zhu, Y. Li, D. Guo, S. Wang, Y. Wei and S. Zhou, Dalton Trans., 2018, 47, 3947
    DOI: 10.1039/C7DT04410K

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