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Issue 10, 2017
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Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(III) complexes

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Abstract

The chemistry of rare-earth carbene and alkylidene complexes including their synthesis, structure and reaction is a challenging issue because of their high reactivity (or instability) and the lack of synthetic methods. In this work, we report the first synthesis of the bridged bis-alkylidene complexes which feature a 2-butene-1,1,4,4-tetraanion and four Sc–C(sp3) bonds by the reaction of 1,4-dilithio-1,3-butadienes with ScCl3. This reaction proceeds via two key intermediates: an isolable scandacyclopentadiene and a proposed scandacyclopropene. The scandacyclopentadiene undergoes β,β′-C–C bond cleavage to generate the scandacyclopropene, which then dimerizes to afford the bridged bis-alkylidene complex via a cooperative double metathesis reaction. Reaction chemistry study of the bridged bis-alkylidene complex reveals their ligand-based reduction reactivity towards different oxidants such as hexachloroethane, disulfide and cyclooctatetraene.

Graphical abstract: Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(iii) complexes

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Publication details

The article was received on 04 May 2017, accepted on 26 Jul 2017 and first published on 31 Jul 2017


Article type: Edge Article
DOI: 10.1039/C7SC02018J
Citation: Chem. Sci., 2017,8, 6852-6856
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    Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(III) complexes

    W. Ma, C. Yu, Y. Chi, T. Chen, L. Wang, J. Yin, B. Wei, L. Xu, W. Zhang and Z. Xi, Chem. Sci., 2017, 8, 6852
    DOI: 10.1039/C7SC02018J

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