Exploring the mechanism of in situ formation of oxalic acid for producing mixed fumarato-oxalato lanthanide (Eu, Tb and Gd) frameworks

Oliveira, Cristiane K.; Vicenti, Juliano Rosa de Menezes; Burrow, Robert A.; Alves, Severino; Longo, Ricardo L.; Malvestiti, Ivani

doi:10.1016/j.inoche.2012.04.036

Cited by 9 publications

(2 citation statements)

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“…In the case of the neodymium nitrate (see Figure 15), the situation is slightly different and more complicated since three different structures are obtained depending on the synthesis conditions. In the presence of oxalic acid, the use of imidazolium ligand in its zwitterionic form [HL] [44,51,52]; (ii) the decarboxylation of the organic species followed by a reductive coupling of the carbon dioxide [53]; (iii) the oxidation of ethanol in the presence of nitrate anions [54]; and (iv) the hydrolysis followed by an oxidation and a decomposition of the organic species [55]. However, in the conditions used here in the presence of nitrates and alcohol, it is difficult to discuss these mechanisms further.…”

Section: Discussionmentioning

confidence: 99%

Elaboration of Luminescent and Magnetic Hybrid Networks Based on Lanthanide Ions and Imidazolium Dicarboxylate Salts: Influence of the Synthesis Conditions

et al. 2016

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Section: Discussionmentioning

confidence: 99%

Elaboration of Luminescent and Magnetic Hybrid Networks Based on Lanthanide Ions and Imidazolium Dicarboxylate Salts: Influence of the Synthesis Conditions

et al. 2016

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“…Notice that these catalysts have distinct activities (Table 6), with MandEu being much more efficient. This may probably be due to their different structures, where EuFum has a metal-organic framework (MOF) structure [25,40,41,42], whereas MandEu is most likely a molecular octacoordinated complex [43,44,45]. The latter is dispersed more efficiently in solution and provide more active sites.…”

Section: Discussionmentioning

confidence: 99%

A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst

et al. 2016

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Secondary and tertiary alcohols synthesized via allylation of aldehydes and ketones are important compounds in bioactive natural products and industry, including pharmaceuticals. Development of a mechanochemical method using potassium allyltrifluoroborate salt and water, to successfully perform the allylation of aromatic and aliphatic carbonyl compounds is reported for the first time. By controlling the grinding parameters, the methodology can be selective, namely, very efficient for aldehydes and ineffective for ketones, but by employing lanthanide catalysts, the reactions with ketones can become practically quantitative. The catalyzed reactions can also be performed under mild aqueous stirring conditions. Considering the allylation agent and its by-products, aqueous media, energy efficiency and use of catalyst, the methodology meets most of the green chemistry principles.

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Ex‐Situ Kinetic Investigations of the Formation of the Poly‐Oxo Cluster U₃₈

Falaise

Volkringer

Hennig

et al. 2015

Chemistry A European J

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The ex-situ qualitative study of the kinetic formation of the poly-oxo cluster U38 , has been investigated after the solvothermal reaction. The resulting products have been characterized by means of powder XRD and scanning electron microscopy (SEM) for the solid phase and UV/Vis, X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and NMR spectroscopies for the supernatant liquid phase. The analysis of the different synthesis batches, stopped at different reaction times, revealed the formation of spherical crystallites of UO2 from t=3 h, after the formation of unknown solid phases at an early stage. The crystallization of U38 occurred from t=4 h at the expense of UO2 , and is completed after t=8 h. Starting from pure uranium(IV) species in solution (t=0-1 h), oxidation reactions are observed with a U(IV) /U(VI) ratio of 70:30 for t=1-3 h. Then, the ratio is inversed with a U(IV) /U(VI) ratio of 25/75, when the precipitation of UO2 occurs. Thorough SEM observations of the U38 crystallites showed that the UO2 aggregates are embedded within. This may indicate that UO2 acts as reservoir of uranium(IV), for the formation of U38 , stabilized by benzoate and THF ligands. During the early stages of the U38 crystallization, a transient crystallized phase appeared at t=4 h. Its crystal structure revealed a new dodecanuclear moiety (U12 ), based on the inner hexanuclear core of {U6 O8 } type, decorated by three additional pairs of dinuclear U2 units. The U12 motif is stabilized by benzoate, oxalates, and glycolate ligands.

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Exploring the mechanism of in situ formation of oxalic acid for producing mixed fumarato-oxalato lanthanide (Eu, Tb and Gd) frameworks

Cited by 9 publications

References 48 publications

Elaboration of Luminescent and Magnetic Hybrid Networks Based on Lanthanide Ions and Imidazolium Dicarboxylate Salts: Influence of the Synthesis Conditions

Elaboration of Luminescent and Magnetic Hybrid Networks Based on Lanthanide Ions and Imidazolium Dicarboxylate Salts: Influence of the Synthesis Conditions

A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst

Ex‐Situ Kinetic Investigations of the Formation of the Poly‐Oxo Cluster U₃₈

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Exploring the mechanism of in situ formation of oxalic acid for producing mixed fumarato-oxalato lanthanide (Eu, Tb and Gd) frameworks

Cited by 9 publications

References 48 publications

Elaboration of Luminescent and Magnetic Hybrid Networks Based on Lanthanide Ions and Imidazolium Dicarboxylate Salts: Influence of the Synthesis Conditions

Elaboration of Luminescent and Magnetic Hybrid Networks Based on Lanthanide Ions and Imidazolium Dicarboxylate Salts: Influence of the Synthesis Conditions

A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst

Ex‐Situ Kinetic Investigations of the Formation of the Poly‐Oxo Cluster U38

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Ex‐Situ Kinetic Investigations of the Formation of the Poly‐Oxo Cluster U₃₈