Lateral metallation and redistribution reactions of sodium ferrates containing bulky 2,6-Diisopropyl- N -(trimethylsilyl)anilide ligands

Maddock, Lewis C. H. and Morton, Rebekka and Kennedy, Alan R. and Hevia, Eva (2021) Lateral metallation and redistribution reactions of sodium ferrates containing bulky 2,6-Diisopropyl- N -(trimethylsilyl)anilide ligands. Chemistry - A European Journal, 27 (61). pp. 15181-15187. ISSN 1521-3765 (https://doi.org/10.1002/chem.202102328)

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Abstract

Alkali-metal ferrates containing amide groups have emerged as regioselective bases capable of promoting Fe−H exchanges of aromatic substrates. Advancing this area of heterobimetallic chemistry, a new series of sodium ferrates is introduced incorporating the bulky arylsilyl amido ligand N(SiMe 3)(Dipp) (Dipp=2,6-iPr 2-C 6H 3). Influenced by the large steric demands imposed by this amide, transamination of [NaFe(HMDS) 3] (HMDS=N(SiMe 3) 2) with an excess of HN(SiMe 3)(Dipp) led to the isolation of heteroleptic [Na(HMDS) 2Fe{N(SiMe 3)Dipp}] ∞ (1) resulting from the exchange of just one HMDS group. An alternative co-complexation approach, combining the homometallic metal amides [NaN(SiMe 3)Dipp] and [Fe{N(SiMe 3)Dipp} 2] induces lateral metallation of one Me arm from the SiMe 3 group in the iron amide furnishing tetrameric [NaFe{N(SiCH 2Me 2)Dipp}{N(SiMe 3)Dipp}] 4 (2). Reactivity studies support that this deprotonation is driven by the steric incompatibility of the single metal amides rather than the basic capability of the sodium reagent. Displaying synergistic reactivity, heteroleptic sodium ferrate 1 can selectively promote ferration of pentafluorobenzene using one of its HMDS arms to give heterotrileptic [Na{N(SiMe 3)Dipp}(HMDS)Fe(C 6F 5)] ∞ (4). Attempts to deprotonate less activated pyridine led to the isolation of NaHMDS and heteroleptic Fe(II) amide [(py)Fe{N(SiMe 3)Dipp}(HMDS)] (5), resulting from an alternative redistribution process which is favoured by the Lewis donor ability of this substrate.

ORCID iDs

Maddock, Lewis C. H., Morton, Rebekka, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015 and Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506;
  • Item type:Article
    ID code:77859
    Dates:
    Date
    Event
    2 November 2021
    Published
    29 July 2021
    Published Online
    29 July 2021
    Accepted
    28 June 2021
    Submitted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:22 Sep 2021 10:40
    Last modified:21 Nov 2024 01:21
    URI:https://strathprints.strath.ac.uk/id/eprint/77859
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