Mono‐ und Diferriophosphane und ‐thioxophosphorane

Abstract

Mono‐ and Diferriophosphanes and ‐thioxophosphoranes Herrn Professor Dr. Ekkehard Lindner zum 60. Geburtstag gewidmet. The substitution of organic substituents in phosphanes or thioxophosphoranes by the 17‐electron fragments CpFe‐(CO) 2 (Fp) leads to isolobal ferriophosphanes or ‐thioxophosphoranes. The mono‐ and diferriophosphanes Fp n PPh 3− n [ n = 1 ( 3 ), 2 ( 4 )] are obtained by deprotonation of the mono‐ and diferriophosphonium salts [Fp n PPh 3− n H]X [ n = 1 ( 1 ), 2 ( 2 )] with DBU. They are oxidized by sulfur giving the mono‐ and diferriothioxophosphoranes Fp n PPh 3− n (S) [ n = 1 ( 5 ), 2 ( 6 )]. Sulfide 5 arises also from the reaction of CpFe(CO) 2 Cl and Ph 2 PH(S)/DBU. The one‐sided decarbonylation reaction of 6 leads to FpFp′PPh(S) ( 7 , Fp′ = CpFeCO). The Fp substituents (17 electrons) in 3–7 coordinate as one‐electron donors to the Ph n P‐ or Ph n P(S) units ( n = 1, 2). The bridging functions in 4 and 6 are hitherto unknown. The molecular structures of the complexes 5–7 were determined by X‐ray structure analyses.