Lanthanum nitridoborates

Nitridoborates of lanthanum and the lanthanides were obtained from reactions of lanthanide metal or lanthanide metal nitride with layer-like (a-)BN at elevated temperatures (3 1200°C). These reactions require elaborated techniques in the inert gas sample-handling and the use of efficient heating sources, such as induction heating. Only some compounds remain stable in this high-temperature segment, and the yields of such reactions are often limited due to the competing stability of binary phases, allowing only the most (thermodynamically) stable compounds to exist. 

The chemistry of lanthanide nitridoborates was developed by the more flexible and more efficient solid-state metathesis route by using nitridoborate salts and a lanthanide trichloride, at reaction temperatures as low as 600 °C. This type of reaction has been previously established and studied in some detail for reactions, such as the synthesis of lanthanide nitrides (LnN). Following this concept, lanthanum nitridoborates are obtained from reactions of lanthanum trichloride and lithium nitridoborate (or calcium nitridoborate), performed in a salt-balanced manner with respect to the formation of the co-produced liCl  

In this exothermic reaction (Fig. 8.8) the [BN2] ions undergo a trimerization to form a cyclic [BsNs] ion with three exocyclic nitrogen atoms (Fig. 8.9). Afterwards La3(B3N6) is washed with water in order to remove liCl. 

For the generation of more nitrogen-rich compounds, a nitride is included in the reaction. This synthesis allows the formation of different nitridoborate (8) ions as well as nitridoborate nitrides (9) [26]  

Metal-rich compounds are readily obtained when a metallothermic reduction is included into the metathesis reaction by using an electropositive metal (10). In addition, metal-rich and nitrogen-rich compounds are obtained when a metal and a metal nitride are employed in reactions (11, 12)  

---

Based on the results of our band-structure calculations we assume that the metal-like properties of lanthanum nitridoborates are related by B-B interactions between adjacent BNx units in structures. 

Structures of the lanthanide nitridoborates appear as layered structures with approximate hexagonal arrangements of metal atoms, and typical coordination preferences of anions. As in many metal nitrides, the nitride ion prefers an octahedral environment such as in lanthanum nitride (LaN). As a terminal constituent of a BNx anion, the nitrogen atom prefers a six-fold environment, such as B-N Lns, where Ln atoms form a square pyramid around N. Boron is typically surrounded by a trigonal prismatic arrangement of lanthanide atoms, as in many metal borides (Fig. 8.10). All known structures of lanthanide nitridoborates compromise these coordination patterns. 

Lanthanide nitridoborates can be divided into three classes salt-like compounds, semiconductors, and conductors or superconductors, as already shown in Fig. 8.7. Salt-like structures are usually transparent materials, marked by the typical color of the lanthanide ion. Here we discuss only nitridoborate compounds of lanthanum. The compounds La3(B3N, ) [27], La5(B3N, )(BN3) [28], Lag(B3N6)(BN3)N [29], and La3(BN3)N all count as salt-like materials, with La, ... 

B3N6] A [BN3] and N (Fig. 8.11). Band-structure calculations performed for La3(B3N5) revealed a band gap in the order of 4 eV. The corresponding nitridoborate oxide La5(BN3)Og [30] is also salt-Hke, owing the typical nitridoborate structure pattern regarding the environment of the [BN3] ion with lanthanum... 

Mixed B-C-N compounds of lanthanum maybe subdivided into La-(BNx), La-(BCx), and La-(CNx) compounds (Fig. 8.15). The chemistry of lanthanide nitridoborates has been developed in some detail and some properties were studied. But still more work is necessary, especially in the field of quaternary Ln-metal-(BNx) compounds. 

---