Isotope-exchange dynamics in isostructural decametalates with profound differences in reactivity

Eric Villa, Christian Andre Ohlin, James Rustad, William Casey

Research output: Contribution to journalArticleResearchpeer-review

37 Citations (Scopus)

Abstract

Rates of oxygen-isotope exchange at all structural sites in two isostructural polyoxometalates, [HxNb10O28](6-x)- and [HxTi2Nb8O28](8-x)-, show that small changes in structure have surprising and profound effects: a single-site substitution of Ti(IV) for Nb(V) inverts the pH dependencies for rates throughout the structures. Within a given structure, all oxygens exhibit similar pH dependencies although they react over a range greater than 104, indicating that pathways involve concerted motions of the entire lattices. Profound sensitivity to changes in structure and composition suggests reaction pathways in polyoxometalate ions will be highly variable even within structural classes.
Original languageEnglish
Pages (from-to)16488 - 16492
Number of pages5
JournalJournal of the American Chemical Society
Volume131
Issue number45
DOIs
Publication statusPublished - 2009
Externally publishedYes

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