The reaction of tetrachlorodiphosphines [Cl2P(CH2)nPCl2; n = 2-4] with fluorous aromatic precursors 4-bromo(perfluorohexyl)benzene and 4-(perfluorohexyl)phenol gave a series of fluorous-tagged diphosphines [(p-C6F13C6H4)2P(CH2)nP(C6H4C6F13-p)2; n = 2-4] and a new diphosphonite [(p-C6F13C6H4O)2P(CH2)3P(OC6H4C6F13-p)2]. The improved synthesis of 1,3-bis(dichlorophosphino)propane (dcpp), involved the facile chlorination of the corresponding primary phosphine with triphosgene. Fluorinated diimines RN=C(CH3)C(CH3)=NR, where R = p-C6H4C6F13 or p-C6H4C8F17 have also been prepared, and were found to be air-stable alternatives to the highly air-sensitive phosphorus-containing ligands. All compounds were characterised by a variety of techniques including NMR, IR, MS and microanalysis. The successful reduction of the phosphine-oxides [(p-C6F13C6H4)2P(O)(CH2)nP(O)(C6H4C6F13-p)2; n = 2,3] with phenylsilane is also presented.