Ferrocenes Bearing Sulfinylamino Groups

1,1′‐Diaminoferrocene ( 2 ) and 1,1′‐bis(trimethylsilylamino)ferrocene ( 3 ) have been converted into sulfinylamines by treatment with thionyl chloride in the presence of triethylamine. In the case of 2 the 1:2 reaction affords 1,1′‐bis(sulfinylamino)ferrocene ( 5 ) and the 1:1 reaction gives 6‐amino‐1‐sulfinylaminoferrocene ( 6 ). Bis(trimethylsilylamino)ferrocene reacts with thionyl chloride in a 1:1 molar ratio to give 1‐sulfinylamino‐6‐(trimethylsilylamino)ferrocene ( 8 ). In contrast, the reaction of N , N′ ‐dilithiobis(trimethylsilylamino)ferrocene ( 4 ) with thionyl chloride gives the [3]ferrocenophane 9 , which contains an N–S(O)–N bridge, rather than sulfinylamines or a sulfur diimide. The molecular structures of 5 and 8 were determined by X‐ray analysis. The 57 Fe NMR chemical shift ( δ = +2597.0 ppm) for 5 indicates the strong π‐acceptor properties of the NSO groups. Dynamic 1 H and 13 C NMR spectra prove the hindered rotation of the NSO group about the C–N bonds in 5 , 6 and 8 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)