Thesis

Advances in alkali-metal-mediated manganation and comparisons with magnesiation

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Awarding institution
  • University of Strathclyde
Date of award
  • 2010
Thesis identifier
  • T12549
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Department, School or Faculty
Abstract
  • The primary aim of this research project was to develop the new concept of Alkali-Metal-Mediated Manganation (AMMMn). Work focused on the reaction of the new Na/Mn alkyl-amido base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a series of organic substrates. Firstly we investigated the reaction of the polymeric dialkyl manganese(II) compound [Mn(CH₂SiMe₃)₂]∞ (1) with a range of Lewis base donors, amines and ketones. The new complexes produced various structural forms ranging from simple monomeric complexes such as [(TMEDA)Mn(CH₂SiMe₃)₂] (2) to more complicated polymeric species such as the dioxane bridged [{(dioxane)[Mn(CH₂SiMe₃)₂]₂}∞] (4). Dialkyl manganese reagent 1 can also function as a deprotonation reagent in its reaction with the primary amine DippNH₂ to afford the trimeric compound [(DippNH)₆Mn₃] (11), while its reaction with benzophenone furnishes the 1,2-addition product [(Me₃SiCH₂)₂Mn₃{μ-OC(CH₂SiMe₃)Ph₂}₄] (13). AMMMn reactions of the synergic base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a variety of functionalised and non-functionalised arene substrates resulted in nine examples of the first reported direct manganations. Highlights include the meta manganation of N, N-dimethylaniline [(TMEDA)Na(TMP)(m-C₆H₄-NMe₂)Mn(TMP)] (21), the para manganation of N, N-diisopropylaniline [(TMEDA)Na(TMP)(p-C₆H₄NiPr₂)Mn(TMP)] (22) and the novel 6-position mangantion of N, N-dimethyl-1-naphthylamine [(TMEDA)Na(TMP){6-(1-Me₂N-C₁₀H₆)}Mn(TMP)] (27). Extending the methodology to Mn(II) based inverse crown complexes proved successful with three new anionic guest molecules, namely a hydride, benzenediide and n-butoxide, successfully being encapsulated within host rings to give three new Mn(II) inverse crown complexes [Na₂Mn₂(μ-H)₂{N(iPr)₂}₄]·(toluene)₂ (31), [(TMEDA)₂Na₂(TMP)₂(1,4-C₆H₄)Mn₂(TMP)₂] (38) and [{(TMEDA)Na(CH₂SiMe₃)(OBu)(o-C₆H₄OMe)Mn}₂] (36) respectively. Remarkably the reaction of the synergic base 16 with the cyclic ether THF results in a new type of cleavage reaction where the C₄ backbone of the THF is cleaved and fourfold deprotonated to furnish a 1, 4-manganated butadiene complex [[(TMEDA)Na(TMP)}₂{1, 4-[Mn(TMP)]₂-C₄H₄}] (42) while the THF O atom is synergically trapped in a separate oxo-inverse crown [Na₂Mn₂(TMP)₄O] (44). The magnetic fingerprints of some of the new Mn(II) compounds are discussed in Chapter 7.
Resource Type
DOI
Date Created
  • 2010
Former identifier
  • 812761

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