The synthesis of bis(organostannyl)ethanes of the types (Ph 2XSnCH 2) 2 ( 1, X = Ph; 2, X = Cl; 3, X = Br; 4, X = I) and (Ph 2XSnCH 2) 2 ( 5, X = Br, 6, X = I) is described. The compounds have been investigated by means of 1H, 13C and 119Sn NMR spectroscopy. 2 reacts with HMPA, [Ph 3P = N = PPh 3] + Cl −, and Ph 4PBr, respectively, to give the 1/1 complexes (Ph 2ClSnCH 2) 2 · HMPA ( 7), [Ph 2ClSnCH 2) 2 · Cl] −[Ph 3PNPPh 3] + ( 8), and [(Ph 2ClSnCH 2) 2 · Br] −[Ph 4P] + ( 9). The formation constant K a for 8 in CDCl 3 solution is 2260 M −1. The structures of 7 and 8 have been determined by X-ray diffraction. That of 7 shows that the two tin atoms are pentacoordinate but are inequivalent as a result of having different coordination sphere; one tin atom is coordinated by the monodentate HMPA (SnO 2.255(3) Å) whereas the other interacts with a bridging Cl (Sn(1); Cl(2) 3.000(1) Å). In the anion of 8, the bis(chlorodiphenylstannyl)ethane may be regarded as an unsymmetrical chelate ligand towards Cl(12) (Sn(1)-Cl(12) 2.83(1), Sn(2)-Cl(12) 2.70(1) Å).