X-RAY PHOTOELECTRON SPECTROSCOPIC CHARACTERIZATION OF [(PT(PPH3)2(MU-3-S))2PTCL2], [(PT2(PPH3)4(MU-3-S)2CU)2(MU-DPPF)]-[PF6]2 [DPPF = FE(C5H4PPH2)2] AND OTHER HETEROMETALLIC AGGREGATES DERIVED FROM [(PT(PPH3)2(MU-S))2]

Lewis acid-base reactions between [{Pt(PPh3)2(mu-S)}2] and [{Cu(NO3)(mu-dppf)}2]-NH4PF6 [dppf = Fe(C5H4PPh2)2] and [PtCl2(NCMe)2] gave hexanuclear [{Pt2(PPh3)4(mu3-S)2Cu}2(mu-dppf)][PF6]2 and trinculear [{Pt(PPh3)2(mu3-S)}2PtCl2] respectively. X-ray photoelectron spectroscopic (XPS) studies of these sulfur aggregates were made together with other known alkylated complexes [Pt2(PPh2)4(mu-S)-(mu-SR)]X (R = Me, X = I; R = CH2Cl, X = Cl; R = CHCl2, X = PF6; R = CH2Ph, X = PF6) and metallated complexes [{Pt2(PPh3)4(mu3-S)2}(x)ML]n+ nX- [M = Ni, L = Ph2PCH2CH2PPh2 (dppe), X = PF6, x = 1; M = Pd2, L = (mu-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.