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    Synthesis and reactivity of a PCcarbeneP cobalt(I) complex: the missing link in the cobalt PXP pincer series (X = B, C, N)


    Sung, Simon and Wang, Qingyang and Krämer, Tobias and Young, Rowan D (2018) Synthesis and reactivity of a PCcarbeneP cobalt(I) complex: the missing link in the cobalt PXP pincer series (X = B, C, N). Chemical Science, 9. pp. 8234-8241. ISSN 2041-6539

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    Abstract

    We report the first example of a cobalt PCcarbeneP pincer complex (1) featuring a central alkylidene carbon donor accessed through the dehydration of an alcoholic POP proligand. Complex 1 shares bonding similarities with cobalt PBP and PNP pincer complexes where the donor atom engages in π-bonding with the cobalt centre, and thus completes the PXP (X = B, C, N) pincer ligand series for cobalt (for X donors that partake in M–L π-bonding). As compared to PBP and PNP pincer complexes, which are known to be good hydride and proton acceptors (respectively), complex 1 is found to be an effective hydrogen atom acceptor. Complex 1 partakes in cooperative ligand reactivity, engaging in several small molecule activations with styrene, bromine, carbon disulphide, phenyl acetylene, acetonitrile, hydrogen, benzaldehyde and water (through microreversibility). The mechanism for the formation of complex 1 is studied through the isolation and computational analysis of key intermediates. The formation of 1 is found to avoid C–H activation of the proligand, and instead proceeds through a combination of O–H activation, hydrogen atom transfer, β-hydride elimination and hydrogen activation processes.

    Item Type: Article
    Additional Information: This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence https://creativecommons.org/licenses/by-nc/3.0/. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes. Cite as: Synthesis and reactivity of a PCcarbeneP cobalt(I) complex: the missing link in the cobalt PXP pincer series (X = B, C, N) S. Sung, Q. Wang, T. Krämer and R. D. Young, Chem. Sci., 2018, 9, 8234 DOI: 10.1039/C8SC02782J
    Keywords: Synthesis; reactivity; PCcarbeneP cobalt(I) complex; cobalt PXP pincer series (X = B, C, N);
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Faculty of Science and Engineering > Research Institutes > Hamilton Institute
    Item ID: 10765
    Identification Number: https://doi.org/10.1039/c8sc02782j
    Depositing User: Tobias Krämer
    Date Deposited: 01 May 2019 15:35
    Journal or Publication Title: Chemical Science
    Publisher: Royal Society of Chemistry
    Refereed: Yes
    URI:

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