Reactions of [Pt 2 (l-S) 2 (PPh 3 ) 4 ] with Ph 3 PbCl, Ph 2 PbI 2 , Ph 2 PbBr 2 and Me 3 PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt 2 (l-S) 2 (PPh 3 ) 4 PbR 3 ] + (R 3 = Ph 3 , Ph 2 I, Ph 2 Br, Me 3 ) isolated as PF 6 À or BPh 4 À salts. In the case of the Me 3 Pb and Et 3 Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt 2 (l-S)(l-SR)(PPh 3 ) 4 ] + (R = Me, Et). X-ray structure determinations on [Pt 2 (l-S) 2 (PPh 3 ) 4 PbMe 3 ]PF 6 and [Pt 2 (l-S) 2 (PPh 3 ) 4 PbPh 2 I]PF 6 have been carried out, revealing different coordination modes. In the Me 3 Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph 2 PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt 2 S 2 } metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt 2 (l-S) 2 (PPh 3 ) 4 PbR 3 ] + display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh 3 in all cases; for R = Ph, loss of PbPh 2 occurs, yielding [Pt 2 (l-S) 2 (PPh 3 ) 3 Ph] + , while for R = Me, reductive elimination of ethane gives [Pt 2 (l-S) 2 (PPh 3 ) 3 PbMe] + , which is followed by loss of CH 4 .