Synthesis, structure, and reactivity of polyoxovanadates in nonaqueous media

Exploration of the nonaqueous chemistry of polyoxovanadates was initiated by studying the following reaction: x $\rm H\sb3V\sb{10}O\sb{28}\sp{3-}$ + y OH$\sp-$ $\to$ 10 $\rm H\sb nV\sb xO\sb m\sp{z-}$ + (y-n) H$\sb2$O involving the addition of (TBA)(OH) to ($\rm H\sb3V\sb{10}O\sb{28}$)(TBA)$\sb3$ in CH$\sb3$CN, where TBA = tetra-n-butylammonium. This resulted in the synthesis and characterization of two types of soluble species: first, reactive isopolyvanadate species which can serve as good starting materials for the development of the synthetic chemistry of covalent polyoxovanadate derivatives; second, species which have structural features normally associated with those present on solid vanadium oxide surfaces. The first species isolated from this reaction was $\rm H\sb2V\sb{10}O\sb{28}\sp{4-}$ as a TBA salt, structural characterization in the solid and solution state reveal that the protonation sites are two OV$\sb2$ oxygens. This anion was found to be unstable in acetonitrile with respect to disproportionation forming two new polyoxovanadates, $\rm V\sb5O\sb{14}\sp{3-}$ and $\rm V\sb{12}O\sb{32}\sp{4-}$.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2011

Author dc:creator

• Yaghi, Omar M.

Contributors dc:contributor

• Klemperer, Walter G.

• Chemistry, Inorganic

Statement dc:rights

• Copyright 1990 Yaghi, Omar M.

Language dc:language

eng

Identifier

AAI9114471
(UMI)AAI9114471

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/20991