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Issue 8, 2005
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Reactions of a {Mo16}-type polyoxometalate cluster with electrophiles: a synthetic, theoretical and magnetic investigation

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Abstract

A medium-nuclearity mixed-valence polyoxomolybdate [H2Mo16O52]10− = {Mo16} (1a) was synthesized using an approach that employed protonated hexamethylenetetramine (HMTAH+) as counter ion and yielded (HMTAH)101a·34 H2O (1). The {Mo16} cluster anion exhibits significant nucleophilicity and traps electrophiles such as divalent transition metal ions, resulting in a family of isostructural compounds based on {Mo16M2}-type anions [M(H2O)8H2Mo16O52]6− (M = FeII (2), MnII (3), CoII (4)). The highly reactive nature of the {Mo16} system is also revealed by rearrangement and decomposition reactions of 1 to either slowly form a sodium-bridged heptamolybdate-based chain compound (5) when left in the reaction solution or, in the presence of very high concentrations of electrophiles, to heptamolybdate-based cluster compounds [M2(H2O)9Mo7O24]2− of the {M2Mo7}-type (M = FeII (6), MnII (7)). Compounds 1–7 were characterised by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, magnetic susceptibility measurements, and density functional theory calculations.

Graphical abstract: Reactions of a {Mo16}-type polyoxometalate cluster with electrophiles: a synthetic, theoretical and magnetic investigation

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Supplementary files

Article information


Submitted
05 Jan 2005
Accepted
02 Feb 2005
First published
17 Mar 2005

Dalton Trans., 2005, 1372-1380
Article type
Paper

Reactions of a {Mo16}-type polyoxometalate cluster with electrophiles: a synthetic, theoretical and magnetic investigation

D. Long, P. Kögerler, L. J. Farrugia and L. Cronin, Dalton Trans., 2005, 1372
DOI: 10.1039/B419301F

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