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2016-02-24

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Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/128584

Structural and magnetic diversity in alkali-metal manganate chemistry: evaluating donor and alkali-metal effects in co-complexation processes

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https://doi.org/10.1002/chem.201504956

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By exploring co-complexation reactions between the manganese alkyl Mn(CH2SiMe3)2 and the heavier alkalimetal alkyls M(CH2SiMe3) (M=Na, K) in a benzene/hexane solvent mixture and in some cases adding Lewis donors (bidentate TMEDA, 1,4-dioxane, and 1,4-diazabicyclo[2,2,2] octane (DABCO)) has produced a new family of alkali-metal tris(alkyl) manganates. The influences that the alkali metal and the donor solvent impose on the structures and magnetic properties of these ates have been assessed by a combination of X-ray, SQUID magnetization measurements, and EPR spectroscopy. These studies uncover a diverse structural chemistry ranging from discrete monomers [(TMEDA) 2MMn(CH2SiMe3)3] (M=Na, 3; M=K, 4) to dimers [{KMn- (CH2SiMe3)3·C6H6}2] (2) and [{NaMn(CH2SiMe3)3}2(dioxane)7] (5); and to more complex supramolecular networks [{NaMn(CH2SiMe3)3}1] (1) and [{Na2Mn2(CH2SiMe3)6- (DABCO)2}1] (7)). Interestingly, the identity of the alkali metal exerts a significant effect in the reactions of 1 and 2 with 1,4-dioxane, as 1 produces coordination adduct 5, while 2 forms heteroleptic [{(dioxane)6K2Mn2(CH2SiMe3)4(O(CH2)2- OCH=CH2)2}1] (6) containing two alkoxide-vinyl anions resulting from a-metalation and ring opening of dioxane. Compounds 6 and 7, containing two spin carriers, exhibit antiferromagnetic coupling of their S=5/2 moments with varying intensity depending on the nature of the exchange pathways.

Matèries

Manganès, Metalls alcalins, Magnetisme

Matèries (anglès)

Manganese, Alkali metals, Magnetism

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Articles publicats en revistes (Química Inorgànica i Orgànica)

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UZELAC, Marina, BORILOVIĆ, Ivana, AMORES, Marco, CADENBACH, Thomas, KENNEDY, Alan r., AROMÍ BEDMAR, Guillem, HEVIA, Eva. Structural and magnetic diversity in alkali-metal manganate chemistry: evaluating donor and alkali-metal effects in co-complexation processes. _Chemistry-A European Journal_. 2016. Vol. 22, núm. 14, pàgs. 4843-4854. [consulta: 23 de gener de 2026]. ISSN: 0947-6539. [Disponible a: https://hdl.handle.net/2445/128584]

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