Transformation n-dimensionaler Integrale

Körber, Karl-Heinz

doi:10.1007/978-3-322-93435-2_5

Cited by 2 publications

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“…Further oxidation of ytterbium and europium to the trivalent state is promoted viz. there is a clear amonolysis tendency with the increasing charge of the cation [81,82]. The procedure is followed by a subsequent annealing process in sealed ampoules, thus it cannot be excluded that ammonia rich phases containing non-coordinating NH 3 molecules are also formed.…”

Section: Low-temperature Oxidationmentioning

confidence: 99%

The Utilization of Solid State Chemistry Reaction Routes as New Syntheses Strategies for the Coordination Chemistry of Rare Earth Amides

Müller‐Buschbaum

2005

Zeitschrift anorg allge chemie

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Solvent free high-temperature reactions in melts are well known procedures in Solid-State Chemistry. Although the reaction conditions are extreme considering the properties of organic ligands they can also be utilized for Coordination Chemistry and offer a fruitful alternative to usual solvent treatments. This includes the chemistry of organic amides of the rare earth elements. The avoidance of any solvent renders novel homoleptic complexes accessible but also implies difficulties bound to the solid state of the reaction mixtures. The high chemical affinity of the rare earth elements towards halides and especially oxygen limits known homoleptic amides obtained via solvent treatments mostly to multi-chelating ligands like porphyrines, calix-pyrroles etc. With no special conditions met like a high steric demand, solvent molecules as cocoordinating partners enforce the formation of heteroleptic species. This influence can be avoided by the use of completely solvent free reactions, such as melt reactions in which a solid is reacted directly with a melt or with a substance under solvothermal conditions. The high reactivity of the rare earth metals allows the direct oxidation with amines and thus to use high-temperature reactions for the formation of rare earth amides. This includes homoleptic com- Die Anwendung Festkörper-chemischer Synthesemethoden als neue Synthesestrategie für die Koordinationschemie von Selten-Erd-AmidenInhaltsübersicht. Solvensfreie Reaktionen bei hohen Temperaturen sind gut bekannte Vorgehensweisen in der Festkörperchemie. Obgleich die Reaktionsbedingungen extrem bezüglich der Eigenschaften organischer Liganden sind, können sie für die Koordinationschemie genutzt werden und bieten eine Erfolg versprechende Alternative zu gewöhnlichen Reaktionen in Lösungsmitteln. Dies schließt die Chemie organischer Selten-Erd-Amide ein. Die Vermeidung jedweder Lösemittel macht neuartige, homoleptische Komplexe zugänglich, sie bringt aber auch Schwierigkeiten mit sich, die mit dem festen Zustand des gesamten Reaktionsgemenges verbunden sind. Die hohe chemische Affinität der Selten-Erd-Elemente zu den Halogenen und allen voran zu Sauerstoff beschränkt die Bildung homoleptischer Amide zumeist auf die Verwendung multichelatisierender Liganden, wie z.B. mit Porphyrinen oder Calix-Pyrrolen. So keine besonderen Bedingungen wie ein hoher sterischer Anspruch eingehalten werden, erzwingen Solvens-Moleküle als co-koordinierende Teilchen die Bildung von heteroleptischen Verbindungen. Dieser Einfluss kann vermieden werden, wenn stattdessen vollständig solvensfreie Synthesen durchgeführt werden. Gerade die Schmelzsynthese bietet solche Möglichkeiten, da ein Feststoff direkt mit einer Schmelze reagiert oder mit einer Substanz unter solvothermalen Bedingungen. Die hohe Reaktivität der Metalle erlaubt deren direkte Oxidation mit Aminen und damit, derar-811pounds from simple ligands. Crystallization under reaction conditions is possible; no re-crystallization step is necessary preventing the risk of a change of the chemical char...

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Section: Low-temperature Oxidationmentioning

confidence: 99%

The Utilization of Solid State Chemistry Reaction Routes as New Syntheses Strategies for the Coordination Chemistry of Rare Earth Amides

Müller‐Buschbaum

2005

Zeitschrift anorg allge chemie

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“…Furthermore, the absence of oxygen is supported by the electron neutrality as well as the oxygen-free synthesis in liquid ammonia, [19] and this therefore renders the identification of the center ion as a nitride ion plausible. The deprotonation of ammonia proceeds more readily with cations of higher charge than alkaline metal ions, [20] but had not yet been observed for the nitride ion. With compound 1 it was shown that with low-temperature oxidation of ytterbium in liquid ammonia, completely different products can be obtained and stabilized than with the direct hightemperature oxidation of a melt synthesis.…”

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confidence: 99%

[Yb₃N(dpa)₆][Yb(dpa)₃]: A Molecular Nitride of a Rare‐Earth Metal with a Yb₃N Unit

Quitmann

Müller‐Buschbaum

2004

Angew Chem Int Ed

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Centered by a nitride ion: The oxidation of ytterbium with 2,2′‐dipyridylamine in liquid ammonia at low temperatures leads to the novel compound [Yb3N(dpa)6][Yb(dpa)3], which is unique among homoleptic dipyridylamides of the rare‐earth metals. The complete deprotonation of NH3 provides the first molecular nitride of a rare‐earth metal with a Yb3N unit (see picture; C blue, N green, Yb silver).

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Transformation n-dimensionaler Integrale

Cited by 2 publications

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The Utilization of Solid State Chemistry Reaction Routes as New Syntheses Strategies for the Coordination Chemistry of Rare Earth Amides

The Utilization of Solid State Chemistry Reaction Routes as New Syntheses Strategies for the Coordination Chemistry of Rare Earth Amides

[Yb₃N(dpa)₆][Yb(dpa)₃]: A Molecular Nitride of a Rare‐Earth Metal with a Yb₃N Unit

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Transformation n-dimensionaler Integrale

Cited by 2 publications

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The Utilization of Solid State Chemistry Reaction Routes as New Syntheses Strategies for the Coordination Chemistry of Rare Earth Amides

The Utilization of Solid State Chemistry Reaction Routes as New Syntheses Strategies for the Coordination Chemistry of Rare Earth Amides

[Yb3N(dpa)6][Yb(dpa)3]: A Molecular Nitride of a Rare‐Earth Metal with a Yb3N Unit

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[Yb₃N(dpa)₆][Yb(dpa)₃]: A Molecular Nitride of a Rare‐Earth Metal with a Yb₃N Unit