MONOFERRIOPHOSPHANES AND DIFERRIOPHOSPHANES AND DITHIOXOPHOSPHORANES

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.