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Title Advances in alkali-metal-mediated manganation and comparisons with magnesiation / Victoria L. Blair.
Name Blair, Victoria L. .
Abstract 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.
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).
Publication date 2010
Name University of Strathclyde. Dept. of Pure and Applied Chemistry.
Thesis note Thesis PhD University of Strathclyde 2010 T12549
System Number 000000293

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