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

Abstract

The rare-earth metal dialkyl complexes supported by a neutral pyrrolyl functionalized β-diketiminato ligand formulated as 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 through the reactions of β-diketimine HL with the rare-earth metal trialkyl complexes RE(CH2SiMe3)3(thf)2 in high yields. Reactivities of 1 with pyridine derivatives, unsaturated substrates and elemental sulfur were investigated with findings of some interesting chemical transformations. The ligand exchange, sp2 and sp3 C-H bond activations occurred in reactions with pyridine derivatives to afford different types of mononuclear rare-earth metal pyridyl complexes 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)). Likewise, an sp C-H bond activation was found in reaction of phenylacetylene with 1c to produce dinuclear erbium alkynyl complex [LEr(CH2SiMe3)(μ-C≡CPh)]2 (5c). The mixed amidinate-β-diketiminato ytterbium complex LYb[(Dipp)NC(CH2SiMe3)N(Dipp)](CH2SiMe3) (6d) was obtained through insertion of bis(2,6-diisopropylphenyl)carbodiimide into the Yb-alkyl bond, as well as via the direct alkane elimination of CH2SiMe3 moiety with bis(2,6-diisopropylphenyl)formamidine to afford 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 give 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 complexes 18 have been determined by the single-crystal X-ray diffraction analyses.

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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, Accepted Manuscript
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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, Accepted Manuscript , DOI: 10.1039/C7DT04410K

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