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An unusual PFO32−-templated “inverse Keggin” polyanion, [Mo12O46(PF)4]4−, has been isolated from the degradation reaction of an {Mo132}-type Keplerate to [PMo12O40]3− by [Cu(MeCN)4](PF6) in acetonitrile. 31P-NMR studies suggest a structure-directing role for [Cu(MeCN)4]+ in the formation of the highly unusual all-inorganic inverse Keggin structure.
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