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

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

doi:10.1021/ja905166c

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

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

Research output: Contribution to journal › Article › Research › peer-review

41 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 language	English
Pages (from-to)	16488 - 16492
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	131
Issue number	45
DOIs	https://doi.org/10.1021/ja905166c
Publication status	Published - 2009
Externally published	Yes

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10.1021/ja905166c

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title = "Isotope-exchange dynamics in isostructural decametalates with profound differences in reactivity",

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.",

author = "Eric Villa and Ohlin, {Christian Andre} and James Rustad and William Casey",

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language = "English",

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journal = "Journal of the American Chemical Society",

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AU - Villa, Eric

AU - Ohlin, Christian Andre

AU - Rustad, James

AU - Casey, William

PY - 2009

Y1 - 2009

N2 - 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.

AB - 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.

UR - http://pubs.acs.org.ezproxy.lib.monash.edu.au/doi/pdf/10.1021/ja905166c

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DO - 10.1021/ja905166c

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EP - 16492

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 45

ER -

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

Abstract

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