Functionalization of Heteropolyanions-Osmium and Rhenium Nitrido Derivatives of Keggin- and Dawson-Type Polyoxotungstates: Synthesis, Characterization and Multinuclear (183W, 15N) NMR, EPR, IR, and UV/Vis Fingerprints

Reaction of K10[α2‐P2W17O61] or K10[α1‐P2W17O61] or [Bu4N][OsCl4N] in a water/methanol mixture, and subsequent precipitation with (Bu4N)Br provided [α2‐P2W17O61{OsVIN}]7− and [α1‐P2W17O61{OsVIN}]7− Dawson structures as tetrabutylammonium salts. Reactions of [(Bu4N)4][α‐H3PW11O39] with either [ReCl3(...

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Bibliographic Details
Published in:Chemistry : a European journal 2006-12, Vol.12 (36), p.9150-9160
Main Authors: Dablemont, Céline, Hamaker, Christopher G., Thouvenot, René, Sojka, Zbigniew, Che, Michel, Maatta, Eric A., Proust, Anna
Format: Article
Language:English
Subjects:
EPR spectroscopy
nitrido
NMR spectroscopy
osmium
polyoxometalates
rhenium
tungsten
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Summary:Reaction of K10[α2‐P2W17O61] or K10[α1‐P2W17O61] or [Bu4N][OsCl4N] in a water/methanol mixture, and subsequent precipitation with (Bu4N)Br provided [α2‐P2W17O61{OsVIN}]7− and [α1‐P2W17O61{OsVIN}]7− Dawson structures as tetrabutylammonium salts. Reactions of [(Bu4N)4][α‐H3PW11O39] with either [ReCl3(N2Ph2)(PPh3)2] or [Bu4N][ReCl4N] are alternatives to the synthesis of [(Bu4N)4][α‐PW11O39{ReVIN}]. 183W and 15N NMR, EPR, IR, and UV‐visible spectroscopies and cyclic voltammetry have been used to characterize these compounds and the corresponding [(Bu4N)4][α‐PW11O39{OsVIN}] Keggin derivative. Spectroscopic characterization of nitrido derivatives provides insight into the electronic structure of polyoxotungstates. The full assignment of the 183W NMR spectra of [PW11O39{OsN}]4− and [α2‐P2W17O61{OsN}]7− is presented, and EPR spectra of [PW11O39{ReN}]4− are discussed and simulated (see figure).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.200600934