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Tetra\u2010<jats:italic>n<\/jats:italic>\u2010butylammonium salts of Keggin\u2010type polyoxoanions, \u03b1\u2010[(C<jats:sub>4<\/jats:sub>H<jats:sub>9<\/jats:sub>)<jats:sub>4<\/jats:sub>N]<jats:sub>4<\/jats:sub>H<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>[XW<jats:sub>11<\/jats:sub>M(H<jats:sub>2<\/jats:sub>O)O<jats:sub>39<\/jats:sub>]\u00b7<jats:italic>n<\/jats:italic>H<jats:sub>2<\/jats:sub>O, X\u00a0=\u00a0P, Si; M<jats:sup>II<\/jats:sup>\u00a0=\u00a0Co, Ni, M<jats:sup>III<\/jats:sup> = Fe, Mn, <jats:italic>x<\/jats:italic> = 0\u22122, <jats:italic>n<\/jats:italic> = 0\u22122, and sandwich\u2010type polyoxoanions, \u03b1\u2010B\u2010[(C<jats:sub>4<\/jats:sub>H<jats:sub>9<\/jats:sub>)<jats:sub>4<\/jats:sub>N]<jats:sub>7<\/jats:sub>H<jats:sub>3<\/jats:sub>[M<jats:sub>4<\/jats:sub>(H<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>(PW<jats:sub>9<\/jats:sub>O<jats:sub>34<\/jats:sub>)<jats:sub>2<\/jats:sub>], M<jats:sup>II<\/jats:sup> = Co, Mn, have been studied by cyclic voltammetry and spectroelectrochemistry. Under the conditions used, the tungsten\u2010oxo framework of the metal substituted Keggin anions could accept up to three electrons in quasi\u2010reversible one\u2010electron consecutive processes. Comparison with the corresponding lacunary anions is presented. Redox processes at the metal centre have been detected for all metals M except Ni. For the anions \u03b1\u2010[XW<jats:sub>11<\/jats:sub>M(H<jats:sub>2<\/jats:sub>O)O<jats:sub>39<\/jats:sub>]<jats:sup><jats:italic>m<\/jats:italic><\/jats:sup><jats:sup>\u2212<\/jats:sup>, the co\u2010existence of species with a different degree of protonation was deduced from cyclic voltammetry results whenever protons were included in the molecular formula. The influence of the solids\u2019 composition on the electrochemical results is stressed. For the sandwich anions, cyclic voltammetry revealed redox processes occurring on the W atoms and also on the metallic belt. Two metal atoms in the belt of the \u03b1\u2010B\u2010[Co<jats:sup>II<\/jats:sup><jats:sub>4<\/jats:sub>(H<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>(PW<jats:sub>9<\/jats:sub>O<jats:sub>34<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sup>10\u2212<\/jats:sup> anion could be electrochemically oxidised to Co<jats:sup>III<\/jats:sup> in two separate steps. A similar result was observed for the Mn<jats:sup>II<\/jats:sup> analogue, but the corresponding first step was not as well defined. Re\u2010oxidation was only detected for the Co anion. This work is the first comparative study of the electrochemical behaviour of such transition metal substituted polyoxotungstates in an organic medium. (\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2004)<\/jats:p>","DOI":"10.1002\/ejic.200300292","type":"journal-article","created":{"date-parts":[[2004,1,27]],"date-time":"2004-01-27T07:00:43Z","timestamp":1075186843000},"page":"619-628","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":68,"title":["Electrochemical Behaviour of First Row Transition Metal Substituted Polyoxotungstates: A Comparative Study in Acetonitrile"],"prefix":"10.1002","volume":"2004","author":[{"given":"Maria\u00a0Salete","family":"Balula","sequence":"first","affiliation":[]},{"given":"Jos\u00e9\u00a0A.","family":"Gamelas","sequence":"additional","affiliation":[]},{"given":"Helena\u00a0M.","family":"Carapu\u00e7a","sequence":"additional","affiliation":[]},{"given":"Ana\u00a0M.\u00a0V.","family":"Cavaleiro","sequence":"additional","affiliation":[]},{"given":"Walkiria","family":"Schlindwein","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2004,1,26]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"Polyoxometalates: From Platonic Solids to Antirectroviral Activity(Eds.: M. 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