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    Access to and Reactivity of Fe 0 , Fe −I , Fe I , and Fe II PC carbene P Pincer Complexes

    Wang, Qingyang and Manzano, Richard A. and Tinnermann, Hendrik and Sung, Simon and Leforestier, Baptiste and Krämer, Tobias and Young, Rowan D. (2021) Access to and Reactivity of Fe 0 , Fe −I , Fe I , and Fe II PC carbene P Pincer Complexes. Angewandte Chemie, 133 (33). pp. 18316-18325. ISSN 0044-8249

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    Despite their promising metal–ligand cooperative reactivity, PCcarbeneP pincer ligands are rarely reported for firstrow transition-metal centres. Using a dehydration methodology, we report access to an Fe0 PCcarbeneP pincer complex (1) that proceeds via an isolated a-hydroxylalkyl hydrido complex (3). Reversible carbonyl migration to the carbene position in 1 is found to allow coordination chemistry and E@H bond addition (E = H, B, Cl) across the iron–carbene linkage, representing a unique mechanism for metal–ligand cooperativity. The PCcarbeneP pincer ligand is also found to stabilize formal FeII, Fe I, and Fe@I oxidation states, as demonstrated with synthesis and characterization of the complexes [11-X]-[BArF 20] (X = Br, I), 12, and K[13]. Compound K[13] is found to be highly reactive, and abstracts hydrogen from a range of aliphatic C@H sources. Computational analysis by DFT suggests that the formal FeI and Fe@I complexes contain significant carbene radical character. The ability of the PCcarbeneP ligand scaffold to partake in metal–ligand cooperativity and to support a range of iron oxidation states renders it as potentially useful in many catalytic applications

    Item Type: Article
    Additional Information: Cite as: Q. Wang, R. A. Manzano, H. Tinnermann, S. Sung, B. Leforestier, T. Krämer, R. D. Young, Angew. Chem. 2021, 133, 18316.
    Keywords: PCcarbeneP pincer ligands; Reactivity of Fe 0;PCcarbeneP
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Faculty of Science and Engineering > Research Institutes > Hamilton Institute
    Item ID: 17438
    Identification Number:
    Depositing User: Tobias Kraemer
    Date Deposited: 17 Aug 2023 11:12
    Journal or Publication Title: Angewandte Chemie
    Publisher: Wiley on line
    Refereed: Yes
    Use Licence: This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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