New triphenylphosphines substituted with the gem-bis(phosphonate) moiety in the form of ethyl esters, tetraethyl [4-(diphenylphosphanyl)benzyl]methylene-bis(phosphonate) (2a) and octaethyl bis[4-(diphenylphosphanyl)benzyl]methylene-bis(phosphonate) (2b), and the corresponding free acids 3a and 3b were prepared by a multi-step synthesis and characterized by multinuclear NMR spectroscopy and mass spectrometry. The ester ligands 2a and 2b were conveniently purified through their borane adducts. The X-ray structure of 2b x 2BH3 x H2O was determined. Coordination properties of new ligands towards Rh(I), Pd(II) and Pt(II) ions were studied. 1H, 31P and 195Pt NMR spectroscopy showed that ligands 2a and 3a form the expected [RhCl(eta2:eta2-cod)(L)] (cod = cycloocta-1,5-diene) and [MCl2(L)2] (M = Pd, Pt) complexes. The compounds 2b and 3b behave as bridging bidentate ligands forming dinuclear complexes of the {[RhCl(eta2:eta2-cod)]2(mu-L-kappa2P,P')} and [M2Cl4(mu-L-kappa2P,P')2] (M = Pd, Pt) type. These findings are consistent with mass spectrometry and far-IR and Raman spectroscopy results. X-Ray structures of trans-[PdCl2(2a-kappaP)2] and cis,trans-[Pt2Cl4(mu-2b-kappa2P,P)2] were determined; the dinuclear complex exhibits a different arrangement on the Pt(II) centres which was observed for the first time in the solid state. Salts of complexes of the free acid 3a are highly soluble in water.