Issue 2, 2000
From the journal:

Journal of the Chemical Society, Dalton Transactions

Polyoxometalates from heteropoly “brown” precursors. A new structural class of mixed valence heteropolytungstates, [(XO4)WIV3WVI17O62Hx]n−

Michael H. Dickman,*a   Tomoji Ozeki,a   Howard T. Evans, Jr.,*a   Chaoying Rong,a   Geoffrey B. Jamesona  and  Michael T. Pope*a  

* Corresponding authors

a Department of Chemistry, Georgetown University, Box 571227, Washington, DC, USA

Abstract

Reduction of the α-Keggin anion [Xn+O4W12O36][8 − n]− (X = H22+, B3+, Si4+) by six electrons results in the known tungsten “brown” species [Xn+O4(H2O)3WIV3WVI9O33][8 − n]− in which three W atoms have been reduced from WVI to WIV, forming a metal–metal bonded triad. The WIV atoms have terminal water coordinated in place of terminal oxo groups. Additional tungstate can condense onto these water molecules in aqueous solution between pH = 4 and 6.5 to form the species reported here, [(XO4)WIV3WVI17O62Hx]y−. The boron derivative (X = B3+) is more stable than the metatungstate (X = H22+), both of which have been characterized by elemental analysis, 183W NMR and X-ray crystal structure analysis. Eight additional tungstate groups condense in the form of a partial Keggin structure containing two triads and one dyad which is rotated 60° relative to a hypothetical α-isomer.

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Article information

DOI
https://doi.org/10.1039/A905539H
Article type
Paper
Submitted
06 Jul 1999
Accepted
16 Nov 1999
First published
13 Jan 2000

J. Chem. Soc., Dalton Trans., 2000, 149-154

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Polyoxometalates from heteropoly “brown” precursors. A new structural class of mixed valence heteropolytungstates, [(XO4)WIV3WVI17O62Hx]n−

M. H. Dickman, T. Ozeki, H. T. Evans, Jr., C. Rong, G. B. Jameson and M. T. Pope, J. Chem. Soc., Dalton Trans., 2000, 149 DOI: 10.1039/A905539H

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