Synthesis and reactions of the ferrocene derived hydroxymethyl phosphine FcCH(CH3)P(CH2OH)2 and its sulfide: crystal structures of [FcCH(CH3)P(S)R2] R=CH2OH, CH2CH2CN and FcCH(CH3)P(S)(CH2O)2PPh (Fc=ferrocenyl)

The racemic ferrocene derived hydroxymethyl phosphine FcCH(CH3)P(CH2OH)2 (1) (Fc=ferrocenyl) was prepared by the reaction of P(CH2OH)3 with [FcCH(CH3) NEt2Me]+I−. The latter was prepared by the reduction of acetyl ferrocene to the corresponding alcohol, which was converted into its acetate and reacted further with diethylamine, followed by methyl iodide. Reaction of 1 with acrylonitrile yielded the phosphine FcCH(CH3)P(CH2CH2CN)2 (2), while reaction of 1 with morpholine yielded FcCH(CH3)P[CH2(NC4H8O)]2 (3). Reactions of compounds 1–3 with elemental sulfur yielded the corresponding phosphine sulfides 4–6. The hydroxymethyl groups of the phosphine sulfide FcCHCH3P(S)(CH2OH)2 (4) reacted readily with PhPCl2 and O(SiMe2Cl)2 forming six- and eight-membered heterocycles FcCH(CH3)P(S)(CH2O)2PPh (7) and FcCH(CH3)P(S)(CH2OSiMe2)2O (8), respectively. The crystal structures of compounds 4, 5 and 7 were determined.