X-Ray photoelectron spectroscopic characterization of [{Pt(PPh ₃ ) ₂ (µ ₃ -S)} ₂ PtCl ₂ ], [{Pt ₂ (PPh ₃ ) ₄ (µ ₃ -S) ₂ Cu} ₂ (µ-dppf)][PF ₆ ] ₂ [dppf = Fe (C ₅ H ₄ PPh ₂ ) ₂ ] and other heterometallic aggregates derived from [{Pt(PPh ₃ ) ₂ (µ-S)} ₂ ]

Lewis acid–base reactions between [{Pt(PPH3)2(µ-S)}2] and [{Cu(NO3)(µ-dppf)}2]–NH4PF6[dppf = Fe(C5H4PPh2)2] and [PtCl2(NCMe)2] gave hexanuclear [{Pt2(PPh3)4(µ3-S)2Cu}2(µ-dppf)][PF6]2 and trinuclear [{Pt(PPh3)2(µ3-S)}2PtCl2] respectively. X-Ray photoelectron spectroscopic (XPS) studies of these sulfur aggregates were made together with other known alkylated complexes [Pt2(PPh3)4(µ-S)(µ-SR)]X (R = Me, X = 1; R = CH2Cl, X = Cl; R = CHCl2, X = PF6; R = CH2Ph, X = PF6) and metallated complexes [{Pt2(PPh3)4(µ-S)2}xML]n+nX–[M = Ni, L = Ph2PCH2CH2PPh2(dppe), X = PF6, x= 1; M = Pd2, L =(µ-Cl)2, X = PF6, x= 2; M = Ag2, X = NO3, x= 2; M = Au, L = PPh3, X = PF6, x= 1; M = Hg, X = PF6, x= 2; M = Hg, L = dppe, X = PF6, x= 1; n= 2 for all M except Au where n= 1]. The observed binding energies are related to the charge distribution and nucleophilicity of the sulfur centres. The possibility of using multinuclear XPS [S(2p), P(2p), Cl(2p), Pt(4f)] to distinguish chemically inequivalent nuclei is examined.