Ferrocenyl hydroxymethylphosphines (η 5-C 5H 5)Fe[η 5-C 5H 4P(CH 2OH) 2] and 1,1′-[Fe{η 5-C 5H 4P(CH 2OH) 2} 2] and their chalcogenide derivatives

Abstract

The ferrocenyl hydroxymethylphosphines FcP(CH 2OH) 2 [Fc=(η 5-C 5H 5)Fe(η 5-C 5H 4)] and 1,1′-Fc′[P(CH 2OH) 2] 2 [Fc′=Fe(η 5-C 5H 4) 2] were prepared by reactions of the corresponding primary phosphines FcPH 2 and 1,1′-Fc′(PH 2) 2 with excess aqueous formaldehyde. The crystal structure of FcP(CH 2OH) 2 was determined and compared with the known ferrocenyl hydroxymethylphosphine FcCH 2P(CH 2OH) 2. The chalcogenide derivatives FcP(E)(CH 2OH) 2 and 1,1′-Fc′[P(E)(CH 2OH) 2] 2 (E=O, S, Se) were prepared and fully characterised. Crystal structure determinations on FcP(O)(CH 2OH) 2 and FcP(S)(CH 2OH) 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-[PtCl 2{FcP(CH 2OH) 2} 2] was prepared by reaction of 2 mol equivalents of FcP(CH 2OH) 2 with [PtCl 2(1,5-cyclo-octadiene)], and was characterised by 31P-NMR spectroscopy and negative ion electrospray mass spectrometry, which gave a strong [M+Cl] − ion.