Abstract
New compounds of the formula C 5H 5Co(CO)C 3F 7X (X = Br, Cl) can be prepared from sodium bromide or chloride and C 5H 5Co(CO)C 3F 7OClO 3, the latter reagent being prepared in situ from C 5H 5Co(CO)C 3F 7I and AgClO 4 in benzene. A similar reaction with sodium cyanide or sodium thiocyanate did not give the monomeric cyanide or thiocyanate compounds: from the thiocyanate reaction a trimer [C 5H 5CoC 3F 7SCN] 3 was formed, and from the cyanide ion reaction the product obtained was a polymeric species [C 5H 5CoC 3F 7CN] x ( x~4.5). The structures of these two species involve bridging CN and SCN groups. A dimeric halogen bridge species [C 5H 5CoC 3F 7I] 2 is also described; this material is interconvertible with C 5H 5Co(CO)C 3F 7I by the equilibrium: 2 C 5H 5Co(CO)C 3F 7I ⇄ 2 CO + (C 5H 5CoC 3F 7I) 2 Several ionic compounds containing perfluoropropyl groups are formed in reactions of C 5H 5Co(CO)C 3F 7I or [C 5H 5CoC 3F 7I] 2 and (C 4H 9) 4N +I −, KCN, or NH 4 +F −. These compounds contain anions of the general formula C 5H 5CoC 3F 7(X,Y) − [X,Y = I 2, (CN) 2, IF] and arise from displacement of a carbonyl or iodine bridge by the halide or cyanide anion.
Published Version
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