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Hexacarbonyltungsten and ‐chromium [M(CO)6; M = W, Cr] react smoothly with perfluoroalkyl (Rf = CF3, C2F5) and trifluorovinyl (Rf = CF=CF2) silanes in the presence of equimolar amounts of fluoride ions with exclusive attack of one of the CO ligands to form the corresponding salts, Cat[(CO)5MC(Rf)O] (Cat = [Me4N]+, [Cs(15‐crown‐5)2]+) which after methylation represent the first hitherto unknown perfluoroorgano‐substituted...
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