Clusters nitride

When reacting Ba dissolved in liquid Na with nitrogen at temperatures not too far from the melting point of the solvent, there was evidence for the formation of Ba-rich nitride clusters prior to the deposition of solid Ba2N [8]. Using both Na as well as a K-Na alloy as solvents, an extensive class of new subnitrides can be prepared. They contain [M6N] octahedra, either discrete or condensed into finite clusters and infinite arrays, respectively. 

Dunsch L, Yang S (2007) Metal nitride cluster fullerenes their current state and future prospects. Small 3 1298-1320. 

The electrochemical properties of TNT-EMFs, M3N C2n n > 39) differ from those of the empty cage fullerenes (see Fig. 6) due to the interaction of the metal cluster with the carbon cage and because the structure of these carbon cages are generally different. As a consequence, the reductive processes are electrochemically irreversible but chemically reversible. The oxidative processes occur at lower potentials because the HOMO orbital is mainly localized on the trimetallic nitride clusters and the HOMO-LUMO gaps in solution are smaller [25,58]. The endohedral metallo-fullerenes M C2n show similar behavior but even smaller HOMO-LUMO gaps [59]. 

Chai Y, Guo T, Jin C et al (1991) Fullerenes with metals inside. J Phys Chem 95 7564-7568 Dunsch L, Yang S (2007) Metal nitride cluster fullerenes their current state and future prospects. Small 3 1298-1320... 

Dunsch L, Krause M, Noack J et al (2004) Endohedral nitride cluster fullerenes. Formation and spectroscopic analysis of L3 xMxN C2n (0 < x < 3 N = 39,40). J Phys Chem Solids 65 309-315... 

The characteristic features of Gd3N Cgg, that is, its reversible behavior in both oxidation and reduction steps and its very low HOMO-LUMO gap were found to be a result of the trimetallic nitride clusters encapsulated in a Cg8 cage, since the... 

The result of intensity alternation for the boron nitride cluster ions is in accordance with the generation of high cluster ion beams MnXn, for several systems (e.g. NaCl, CuBr or Csl26 49) by other methods of cluster formation such as by quenching condensation in a cold rare gas or by ion bombardment of hahdes. 

The removal of the O atom to form a nitride cluster is a relatively common reaction path for cluster nitrosyls. Several examples have been reported and in general the O atom is removed by reaction with CO to produce C02 (equations 53 and 54). 

The nitride cluster in TNT EMFs can also be viewed as a whole, which always gives six electrons to the carbon cage [121], This is interpreted by the high electron affinity of the //,-Cso cage six electrons are necessary to make it the most stable hexa-anion. Because N prefers to take the -3 valence, each metal in M3N has a +3 valence. Therefore, it is easy to understand why Sm, Eu, and Yb have not been trapped as TNT EMFs because they can donate only two electrons from their 6s orbitals. 

Melin, F., Chaur, M.N., Engmann, S. et al. (2007) The large Nd3N C2 (40 < = n < = 49) cluster fullerene family preferential templating of a Cgg cage by a trimetallic nitride cluster. Angewandte Chemie International Edition, 46, 9032-9035. 

Cai, T., Xu, L., Shu, C. et al. (2008) Selective formation of a symmetric ScsNOCyg bisadduct adduct docking controlled by an internal trimetallic nitride cluster. Journal of the American Chemical Society, 130, 2136-2137. 

The butterfly nitride clusters are active with H2 in the production of NH, NH2-containing clusters, and eventually to NHj, and they may serve as models for the reduction of NO with H2 and CO. 

The IR spectra of endohedral Li3 xMxN C80, where 0 < x < 3, M = Sc, Y, Tb, Ho or Er, include vibrations of an encaged trimetal nitride cluster.2 The Raman spectra of the D2d symmetry species M2 C84, where M = Sc, Y or Dy, show three groups of metal-cage modes in the range 35-200 cm-1. Variable-temperature data for M = Y shows that there is an order/disorder transition near 150 K.3... 

FELIX is also shown schematically in Fig. 1.19. This method of infrared resonance enhanced multiphoton ionization (IR-REMPI) has been successfully applied to study fullerenes, metal carbide, metal oxide, and metal nitride clusters [126,128-130] as well as metal-adsorbate complexes [131]. 

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