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Keywords = magnesiates

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29 pages, 3949 KB  
Article
Direct Synthesis of Benzhydryl-Functionalized 3,4-Dihydropyridin-2-ones from 2-Pyridones and Their Use in the Formation of Bridged δ-Lactams
by Zofia M. Myk, Jacek G. Sośnicki and Łukasz Struk
Molecules 2024, 29(22), 5274; https://doi.org/10.3390/molecules29225274 - 7 Nov 2024
Cited by 1 | Viewed by 1715
Abstract
A method for the synthesis of C4-benzhydryl-functionalized 3,4-dihydropyridin-2-ones using complementary addition of benzhydryllithium and/or benzhydrylmagnesiate reagents to 2-pyridones, with high regioselectivity triggered by substituents, is described. A partially stereoselective cyclization was successfully demonstrated using TfOH and/or TIPSOTf as Brønsted and Lewis acids, respectively, [...] Read more.
A method for the synthesis of C4-benzhydryl-functionalized 3,4-dihydropyridin-2-ones using complementary addition of benzhydryllithium and/or benzhydrylmagnesiate reagents to 2-pyridones, with high regioselectivity triggered by substituents, is described. A partially stereoselective cyclization was successfully demonstrated using TfOH and/or TIPSOTf as Brønsted and Lewis acids, respectively, leading to C6-phenyl-functionalized 7,8-benzomorphanones. It is also shown that the use of functionalized δ-enelactams obtained with an active methoxy-substituted benzyl group at C3 enabled the preparation of a new C3–C6 bridged system within the δ-lactam framework. Full article
(This article belongs to the Section Organic Chemistry)
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17 pages, 3906 KB  
Article
Redox Hyperactive MOF for Li+, Na+ and Mg2+ Storage
by Hristo Rasheev, Agnieszka Seremak, Radostina Stoyanova and Alia Tadjer
Molecules 2022, 27(3), 586; https://doi.org/10.3390/molecules27030586 - 18 Jan 2022
Cited by 8 | Viewed by 3388
Abstract
To create both greener and high-power metal-ion batteries, it is of prime importance to invent an unprecedented electrode material that will be able to store a colossal amount of charge carriers by a redox mechanism. Employing periodic DFT calculations, we modeled a new [...] Read more.
To create both greener and high-power metal-ion batteries, it is of prime importance to invent an unprecedented electrode material that will be able to store a colossal amount of charge carriers by a redox mechanism. Employing periodic DFT calculations, we modeled a new metal-organic framework, which displays energy density exceeding that of conventional inorganic and organic electrodes, such as Li- and Na-rich oxides and anthraquinones. The designed MOF has a rhombohedral unit cell in which an Ni(II) node is coordinated by 2,5-dicyano-p-benzoquinone linkers in such a way that all components participate in the redox reaction upon lithiation, sodiation and magnesiation. The spatial and electronic changes occurring in the MOF after the interaction with Li, Na and Mg are discussed on the basis of calculated electrode potentials versus Li0/Li+, Na0/Na+ and Mg0/Mg2+, respectively. In addition, the specific capacities and energy densities are calculated and used as a measure for the electrode applicability of the designed material. Although the highest capacity and energy density are predicted for Li storage, the greater structural robustness toward Na and Mg uptake suggests a higher cycling stability in addition to lower cost. The theoretical results indicate that the MOF is a promising choice for a green electrode material (with <10% heavy metal content) and is well worth experimental testing. Full article
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13 pages, 38242 KB  
Article
Magnesium Insertion and Related Structural Changes in Spinel-Type Manganese Oxides
by Ana Robba, Elena Tchernychova, Jan Bitenc, Anna Randon-Vitanova and Robert Dominko
Crystals 2021, 11(8), 984; https://doi.org/10.3390/cryst11080984 - 19 Aug 2021
Cited by 3 | Viewed by 3350
Abstract
Commercial LiMn2O4 powder was used as the base material for probing magnesiation, cycling behavior, and structural stability/changes in (MgxLi1-x)Mn2O4 spinel cathodes in aqueous Mg(NO3)2 and non-aqueous Mg(TFSI)2/diglyme and [...] Read more.
Commercial LiMn2O4 powder was used as the base material for probing magnesiation, cycling behavior, and structural stability/changes in (MgxLi1-x)Mn2O4 spinel cathodes in aqueous Mg(NO3)2 and non-aqueous Mg(TFSI)2/diglyme and Mg(Mg(HFIP)2 − 2Al(HFIP)3/diglyme electrolytes. Each of the samples was delithiated and, then, magnesiated electrochemically in the corresponding electrolyte. The electrochemical activity of the cathode cycled in aqueous electrolyte showed high reversibility during the oxidation process; however, large polarization and a relatively fast capacity fading were the culprits of the system. Cycling in Mg(TFSI)2/diglyme electrolyte solution resulted in much lower initial specific capacity compared to an aqueous counterpart, as well as a much faster failure. On the other hand, cycling in Mg(HFIP)2 − 2Al(HFIP)3/diglyme electrolyte solution demonstrated excellent cycling performance with very low polarization in the first cycles. The observed voltages for this system were near theoretical values for the Mg insertion. Although the electrochemical measurements suggest reversible magnesiation, detailed structural and analytical STEM investigation revealed the differences in the atomic structure and Mn valence of all three cathode samples upon cycling. The electrolytes’ influence on the structural rearrangement during Mg insertion is discussed for each of the three systems. Full article
(This article belongs to the Special Issue Lithium Transition Metal Oxides)
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