Intercalation of alkylamines

A. Matsumoto, T. Odani, K. Sada, M. Miyata, K. Tashiro, Intercalation of Alkylamines into an Organic Polymer Crystal , Nature, 405, 328 (2000)... 

Poojary, D.M. and Clearfield, A., Coordinative Intercalation of Alkylamines into Layered Zinc... 

The alkylammonium derivatives of magadiite also show different interla-mellar structures. Due to pH = 7.5-8 and initial concentrations of 0.1 mol/L, the exchange of sodium ions is accompanied by the intercalation of alkylamines because of the following equilibrium ... 

Matsumoto, A., Odani, T, Sada, K., Miyata, M., Tashiro, K. Intercalation of alkylamines into an organic polymer crystal. Nature, 405, 328-330 (2000). 

Y. Matsuo, T. Miyabe, T. Fukutsuka and Y. Sugie, Preparation and characterization of alkylamine-intercalated graphite oxide. Carbon, 45, 1005-1012 (2007). 

Considerable attention has been devoted to the study of intercalation compounds of the dichalcogenides (Whittingham, 1978 Subba Rao Shafer, 1979). Intercalation compounds of dichalcogenides can be divided into three categories (a) compounds with Lewis base type molecules such as ammonia, n-alkylamines, pyridines etc. (b) compounds with metal cations or molecular cations, Li, Na, K, etc., or [(C5H5)2Co]" and (c) compounds containing both cations and neutral polar (solvated) molecules in the van der Waals gap. 

Figure 8.7 Structures of TaS2-n-alkylamine intercalates (a) bilayer and (b) monolayer configuration of the intercalated amine.

The dichalcogenides of group VI do not readily form intercalates with organic molecules. But n-alkylammonium compounds can be prepared by ion-exchange reactions of the hydrated sodium intercalation compounds such as Na j(H20)o g M0S2. Alkylammonium compounds prepared by this route show lattice expansions that depend on the alkyl chain length, very similar to the MX2-n-alkylamine systems described above. This raises the fundamental question whether protonated amines are the actual intercalated species in both the cases, involving reduction of the host. In fact, this constitutes the basis of the new model for the intercalation reaction in MX2 proposed by Schollhorn (1980). 

Zr(P04NH4)2-H20. The same compound is formed by ammonium ion exchange with Q -Zr(P04)2K2-H20. Heat treatment of the ammonium exchanged form at 300 °C gives back the hydrogen phosphate. Primary alkylamines react very readily to form bilayer intercalation compounds analogous to those formed by clays (the layer area per proton is 24 A ). 

Reactions with Lewis bases are the other major class of redox intercalation reactions that have been explored with the FeOCl lattice. Pyridine, for example, reacts with FeOCl to form two compounds, (py)i/4FeOCl and (pyji/sFeOCl. Reactions of FeOCl with ammonia and alkylamines are among the earliest reported intercalation reactions of compounds with neutral layers. ... 

Nesper and co-workers [219, 248] synthesized nanotubules of alkylammonium intercalated VO by hydrothermal means. The vanadium alkoxide precursor was hydrolyzed in the presence of hexadecylamine and the hydrolysis product (lamellar structured composite of the surfactant and the vanadium oxide) yielded VO, nanotubes along with the intercalated amine under hydrothermal conditions (Figure 8.27(a) and (b)). The interesting feature of this vanadium oxide nanotube is the presence of vanadium in the mixed valent state, thereby rendering it redox-active. The template could not be removed by calcination as the structural stability was lost above 250 °C. Nevertheless, it was possible to partially extract the surfactant under mildly acidic conditions. These workers have later shown that the alkylamine intercalated in the intertubular space could be exchanged with other alkylamines of varying chain lengths as well as a,co-diamines [248]. The distance... 

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