Detailed 17O NMR investigations of hydrolytic aggregation and base degradation in non-aqueous tungstate chemistry have led to the development of a new approach to the synthesis of mono-substituted {MW5} Lindqvist-type tungstates, providing insights into solution speciation and access to the first-row M(II) transition-metal derivatives [(MW5O18H)2]6– (M = Mn, Fe, Co, Ni, Zn). This family of polyoxometalates provides rich opportunities for reactivity studies and some highlights will be described. The MOM bridges in the dimeric anions with M = Fe, Co, Ni, Zn are cleaved by ligands to give the adducts [LMW5O18H]3–, whereas the manganese dimer crystallised intact from pyridine. Mn(III) species are produced by air-oxidation of [(MnW5O18H)2]6– and the adducts [LMnW5O18]3– (L = py, dmf) have been structurally characterised, while methylated FeOW bridges feature in structurally characterised [(FeW5O18H)(FeW5O18Me)]4– and [(µ-O)( FeW5O18Me2)2]4– obtained by oxidation of [(FeW5O18H)2]6–. Attempts to identify possible peroxide derivatives formed in reactions with O2and H2O2 will be described, as will the investigation of higher oxidation state M(IV) and M(V) derivatives, including the synthesis and reactivity of the new Re(V) anion [ReW5O19]3–. The general pattern of reactivity and structural interconversions for {MW5} Lindqvist anions that is emerging from these studies will be presented

New structural and reactivity patterns for {MW5} Lindqvist-type anions

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