Ferrocenyl Sulfinylimide and Diferrocenyl Sulfurdiimide, Fc-NSO and Fc(NSN)Fc

Abstract

Abbreviations and Nomenclature: Fc = η¹‐ferrocenyl, CpFe(C₅H₄‐); Cp = η⁵‐cyclopentadienyl, η⁵‐C₅H₅. Compounds containing the —NSO group are designated as either thionylimides, sulfinylimides or N‐sulfinylamines. The systematic name is imido oxo sulfuranes(IV). The reactions of ferrocenylamine, FcNH₂ (1), with thionyl chloride and sulfur dichloride in hexane solution in the presence of triethylamine lead to the title compounds FcNSO (2) and Fc(NSN)Fc (3), respectively, 2 and 3 have also been obtained in reactions of the silylated ferrocenylamine, FcNH(SiMe₃) (1b), with thionyl chloride. The ferrocenyl sulfinylimide 2 has been converted to sulfurdiimides such as Fc(NSN)Fc (3) and Fc(NSN)R (R = ^tBu (4a), SiMe₃ (4b)) by reaction with the lithium derivative of silylated amines, LiN(SiMe₃)R (R = Fc, ^tBu, SiMe₃). The new ferrocenyl compounds 2–4 have been characterized by their NMR spectra, and their electrochemical behaviour has been studied. The molecular structure of FcNSO (2) has been determined by an X‐ray structure analysis; the sulfinylimide has the Z configuration, and the —NSO group is coplanar with the cyclopentadienyl ring to which it is attached.