Heterobimetallic platinum-bismuth aggregates derived from [Pt-2(mu-S)(2)(PPh3)(4)]

The metalloligand [Pt-2(mu-S)(2)(PPh3)(4)] reacts with Bi(S2CNEt2)(3) or Bi(S2COEt)(3) in methanol to produce the orange cationic adducts [Pt-2(mu-S)(2)(PPh3)(4)Bi(S2CNEt2)(2)](+) and [Pt-2(mu-S)(2)(PPh3)(4)Bi(S2COEt)(2)](+), respectively, isolated as their hexafluoro phosphate salts. An X-ray structure determination on [Pt-2(mu-S)(2)(PPh3)(4)Bi(S2CNEt2)(2)]PF6 reveals the presence of a six-coordinated bismuth centre with an approximately nido-pentagonal bipyramidal coordination geometry. Fragmentation pathways for both complexes have been probed using electrospray ionisation mass spectrometry; ions [Pt-2(mu-S)(2)(PPh3)(2)Bi(S2CXEtn)(2)](+) (X = O, n = 1, X = N, n = 2) are formed by selective loss of two PPh3 ligands, and at higher cone voltages the species [(Ph3P)PtS2Bi](+) is observed. Ions formed by loss of CS2 are also observed for the xanthate but not the dithiocarbamate ions. (c) 2005 Elsevier B.V. All rights reserved.