Eine Festkörper-Metathese-Route zur Synthese von Nitridoboraten des Lanthans

Jing, Hao; Blaschkowski, Björn; Meyer, H.‐Jürgen

doi:10.1002/1521-3749(200209)628:9/10<1955::aid-zaac1955>3.0.co;2-m

Cited by 15 publications

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“…Transition metals do not tend to form nitridoborate compounds, because electrons in BN bonds can have a reducing effect on 3d metal ions. Therefore, Ni 2+ in NiCl 2 is readily reduced by Li 3 BN 2 at 300–400 °C to the metal 38. Transition metals nevertheless can occur in pseudo‐ternary nitridoborate or ternary dicarbide compounds.…”

Section: Discussionmentioning

confidence: 99%

“…Metathesis reactions between LaCl 3 and Li 3 BN 2 have turned out to be an efficient method for the preparation of nitridoborates of lanthanum 38. The Li 3 BN 2 , required as starting material is produced from a 1:1 mixture of Li 3 N and BN in a tantalum ampoule (at 750 °C) or by means of a microwave synthesis in a silica ampoule.…”

Section: Preparative Routesmentioning

confidence: 99%

“…The structure of La 3 Ni 2 (BN) 2 N contains additional LaN layers compared with that of LaNi(BN). Our attempts to reproduce the synthesis from the elements and BN resulted in impure products with transition temperatures of 12 K. Only the application of a metathesis reaction based on Li 3 BN 2 and LaCl 3 resulted in X‐ray‐pure products38 on which transition temperatures of 14 K were measured (Figure 18). 54…”

Section: Metal‐rich Nitridoborate Compounds and Their Nitride Derimentioning

confidence: 99%

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Nitridoborates of the Lanthanides: Synthesis, Structure Principles, and Properties of a New Class of Compounds

Blaschkowski

Jing

Meyer

2002

Angew. Chem. Int. Ed.

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Investigations of the nitridoborates of lanthanides (Ln) have progressed significantly during the last few years. New compounds have been synthesized and characterized and are presented here together with some of their properties. Currently two distinct methods serve for the preparation of nitridoborate compounds; either hexagonal boron nitride undergoes a fragmentation through the reaction with LnN, or dinitridoborate ions are converted into other nitridoborate ions. Lanthanide nitridoborates contain molecular anions such as [BN]n-, [BN2]3-, [B2N4]8-, [B3N6]9-, and [BN3]6- which may occur in combinations with other nitridoborates or with additional nitride ions. In crystal structures of lanthanide nitridoborates these anions are arranged in layers and are surrounded by metal atoms in a characteristic fashion. Terminal N atoms are capped by metal atoms forming a square-pyramid, and B atoms prefer a trigonal-prismatic environment of metal atoms. Nitridoborates form saltlike as well as metal-rich compounds and have the potential to show a lot of what are considered to be important solid-state properties, thus they have a good chance to establish their position within the group of relevant materials.

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Section: Discussionmentioning

confidence: 99%

Section: Preparative Routesmentioning

confidence: 99%

Section: Metal‐rich Nitridoborate Compounds and Their Nitride Derimentioning

confidence: 99%

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Nitridoborates of the Lanthanides: Synthesis, Structure Principles, and Properties of a New Class of Compounds

Blaschkowski

Jing

Meyer

2002

Angew. Chem. Int. Ed.

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“…2002, 114 [49] analoges Ca(BN) erhalten, sondern Ca 3 (BN 2 ) 2 und CaB 6 . Bei CaNi (BN) BN 2 und LaCl 3 ergab rˆntgenographisch reine Produkte, [38] an denen Sprungtemperaturen von 14 K gemessen wurden (Abbildung 18). [50] Aus Pulver-Neutronenbeugungsanalysen wurden f¸r La 3 Ni 2 (BN) 2 N 1Àz ein Stickstoffdefizit von z 0.09 und B-N-Bindungsl‰ngen von 144 pm ermittelt.…”

Section: Verbindungen Mit Dem Bn-ionunclassified

Nitridoborate der Lanthanoide: Synthesewege, Strukturprinzipien und Eigenschaften einer neuen Verbindungsklasse

2002

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AUFSaeTZE H.-J. Meyer et al. nitriden oktaedrische L¸cken (Abbildung 1). Bor ist trigonalprismatisch von Metallatomen umgeben. Dabei sind die Boratome zu unendlichen gewinkelten Str‰ngen verkn¸pft (B-B 184 pm in Nb 2 BN). Analoge Str‰nge aus B-Atomen treten in Metallboriden, z. B. in CrB [11] und FeB, auf. Abbildung 1. Ausschnitt aus der Struktur von Nb 2 BN mit N-Atomen (schwarz) in oktaedrischen L¸cken und B-Atomen (wei˚) trigonalprismatisch von Nb-Atomen (grau) umgeben. 1.2. Nitridoborate der Alkali-und Erdalkalimetalle Alkali-und Erdalkalimetalle bilden salzartige Verbindungen mit dem linearen Dinitridoborat-Ion. [12] Das [NBN] 3À -Ion enth‰lt B-N-Doppelbindungen mit Bindungsl‰ngen von etwa 135 pm und ist isoelektronisch zu [C 3 ] 4À (C-C-Bindungs-l‰nge 135 pm in Ca 3 Cl 2 C 3 [13] und 133 pm in Mg 2 C 3 [14] ), [CBN] 4À (C-B-Bindungsl‰nge 144 pm, B-N-Bindungs-l‰nge 138 pm in Ca 3 Cl 2 CBN [15] ) und CO 2 . Zu den am einfachsten zusammengesetzten Verbindungen mit Dinitridoborat-Ionen z‰hlen Li 3 BN 2 , [2] Na 3 BN 2 [16] und Verbindungen des Typs E 3 (BN 2 ) 2 mit E Ca, Sr, Ba [3, 17±19] und Eu [20] (Abbildung 2). Von Li 3 BN 2 sind zwei Phasen bekannt, die sich durch die relativen Anordnungen von Li und [BN 2 ] 3À unterscheiden. Beim Erhitzen geht a-Li 3 BN 2 bei etwa 862 8C in b-Li 3 BN 2 ber, welches bei 916 8C schmilzt. [21] Na 3 BN 2 wurde durch Hochdrucksynthese hergestellt. Nitridoborat-Nitride vom Typ E 3 (BN 2 )N sind f¸r E Mg [22] und Ca [23] belegt. Mg 3 (BN 2 )N ist in eine Hochdruckform transformierbar, deren Struktur (Raumgruppe Pmmm) [24] mit der in Abbildung 2 gezeigten Struktur von Ca 3 (BN 2 )N (Raumgruppe P4/ mmm) topologisch identisch ist. Einige dieser Dinitridoborate haben ihr Potenzial in der Synthese unter Beweis gestellt. So werden Ca 3 (BN 2 ) 2 und Mg 3 (BN 2 )N in der Technik als Fluss-Katalysatoren f¸r die 3470

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“…A third type of interaction between (BN) π* and Ni orbitals represents the slightly occupied conduction bands. CaNiBN exhibits temperature independent paramagnetism and no superconducting transition down to 4 K. of rare earth nitridoborates was achieved by exothermic solid state metathesis reactions using Li 3 BN 2 and RECl 3 as starting materials [9]. Nitridoborates of lanthanum occur as salt-like compounds such as RE 3 (B 3 N 6 ) RE ϭ La, Ce [10], Pr [11], Nd, Sm, Gd [12], La 5 (B 3 N 6 )(BN 3 ) [13] or La 6 (B 3 N 6 )(BN 3 )N [14] and as metal-rich compounds like La 3ϩx (B 2 N 4 )N x for x ϭ 0 [15,13], 1 [16], 2 [17] with La 3ϩ and (B 2 N 4 ) 8Ϫ ions with one surplus electron per formula unit in metal dominated energy bands.…”

Section: Introductionmentioning

confidence: 99%

Electronic Conditions of Diatomic (BN) Anions in the Structure of CaNiBN

Blaschkowski¹,

Meyer²

2002

Z. anorg. allg. Chem.

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CaNiBN was synthesized from Ca, Ni and BN in sealed tantalum containers at 1000°C. The structure was determined by single-crystal X-ray diffraction (P4/nmm, Z ϭ 2, a ϭ 353.24(3) pm, c ϭ 763.59(9) pm, R 1 ϭ 0.019, wR 2 ϭ 0.045 for all collected independent reflections). CaPdBN was synthesized after the same method, and a powder pattern was indexed isotypically (P4/nmm, a ϭ 377.38(1) pm, c ϭ 760.95(4) pm). The CaNiBN structure contains (BN) units with BϪN bond lengths of 138.1(4) pm. If the (BN) unit in CaMBN (M ϭ Ni, Pd) is replaced by (C 2 ), the structure can be considered as being isotypic with the structure of UCoC 2 . Die elektronische Situation zweiatomiger (BN)-Anionen in der Struktur von CaNiBNInhaltsübersicht. CaNiBN wurde aus Ca, Ni and BN in verschweiß-ten Tantal-Behältern bei 1000°C dargestellt. Die Struktur wurde durch Einkristall-Röntgenbeugung aufgeklärt (P4/nmm, Z ϭ 2, a ϭ 353,24(3) pm, c ϭ 763,59(9) pm, R 1 ϭ 0,019, wR 2 ϭ 0,045 für alle erfassten unabhängigen Reflexe). Nach der gleichen Synthesemethode wurde CaPdBN dargestellt, dessen Pulverdiagramm isotyp indiziert wurde (P4/nmm, a ϭ 377.38(1) pm, c ϭ 760.95(4) pm). Die Struktur von CaNiBN enthält (BN)-Einheiten mit BϪN-Bindungslängen von 138.1(4) pm. Die Strukturen CaMBN (M ϭ Ni, Pd) können als isotyp zur UCoC 2 -Struktur betrachtet werden, wenn die (BN)-Einheit durch (C 2 ) ersetzt wird.

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Eine Festkörper-Metathese-Route zur Synthese von Nitridoboraten des Lanthans

Cited by 15 publications

References 18 publications

Nitridoborates of the Lanthanides: Synthesis, Structure Principles, and Properties of a New Class of Compounds

Nitridoborates of the Lanthanides: Synthesis, Structure Principles, and Properties of a New Class of Compounds

Nitridoborate der Lanthanoide: Synthesewege, Strukturprinzipien und Eigenschaften einer neuen Verbindungsklasse

Electronic Conditions of Diatomic (BN) Anions in the Structure of CaNiBN

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