Ferrocenyl hydroxymethylphosphines (η5-C5H5)Fe[η5-C5H4P(CH2OH)2] and 1,1′-[Fe{η5-C5H4P(CH2OH)2}2] and their chalcogenide derivatives

The ferrocenyl hydroxymethylphosphines FcP(CH2OH)2 [Fc=(η5-C5H5)Fe(η5-C5H4)] and 1,1′-Fc′[P(CH2OH)2]2 [Fc′=Fe(η5-C5H4)2] were prepared by reactions of the corresponding primary phosphines FcPH2 and 1,1′-Fc′(PH2)2 with excess aqueous formaldehyde. The crystal structure of FcP(CH2OH)2 was determined and compared with the known ferrocenyl hydroxymethylphosphine FcCH2P(CH2OH)2. The chalcogenide derivatives FcP(E)(CH2OH)2 and 1,1′-Fc′[P(E)(CH2OH)2]2 (E=O, S, Se) were prepared and fully characterised. Crystal structure determinations on FcP(O)(CH2OH)2 and FcP(S)(CH2OH)2 were performed, and the hydrogen-bonding patterns are compared with related compounds. The sulfide shows no hydrogen-bonding involving the phosphine sulfide group, in contrast to other reported ferrocenyl hydroxymethylphosphine sulfides. The platinum complex cis-[PtCl2{FcP(CH2OH)2}2] was prepared by reaction of 2 mol equivalents of FcP(CH2OH)2 with [PtCl2(1,5-cyclo-octadiene)], and was characterised by 31P-NMR spectroscopy and negative ion electrospray mass spectrometry, which gave a strong [M+Cl]− ion.