Rose, Sarah L.Henderson, WilliamNicholson, Brian K.Hor, T.S. Andy2009-10-132009-10-132009Rose, S. L., Henderson, W., Nicholson, B. K. & Hor, A. T. S. (2009). Thallium(III) complexes of the metalloligands [Pt₂(μ-S)₂(PPh₃)₄] and [Pt₂(μ-Se)₂(PPh₃)₄]. Inorganica Chimica Acta, 362(15), 5237-5244.https://hdl.handle.net/10289/3248Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with the diarylthallium(III) bromides Ar₂TlBr [Ar = Ph and p-ClC₆H₄] in methanol gave good yields of the thallium(III) adducts [Pt₂(μ-S)₂(PPh₃)4TlAr₂]⁺, isolated as their BPh₄⁻ salts. The corresponding selenide complex [Pt₂(μ-Se)₂(PPh₃)₄TlPh₂]BPh₄ was similarly synthesised from [Pt₂(μ-Se)₂(PPh₃)₄], Ph₂TlBr and NaBPh₄. The reaction of [Pt₂(μ-S)₂(PPh₃)₄] with PhTlBr₂ gave [Pt₂(μ-S)₂(PPh₃)₄TlBrPh]⁺, while reaction with TlBr₃ gave the dibromothallium(III) adduct [Pt₂(μ-S)₂(PPh₃)₄TlBr₂]⁺[TlBr₄]⁻. The latter complex is a rare example of a thallium(III) dihalide complex stabilised solely by sulfur donor ligands. X-ray crystal structure determinations on the complexes [Pt₂(μ-S)₂(PPh₃)₄TlPh₂]BPh₄, [Pt₂(μ-S)₂(PPh₃)₄TlBrPh]BPh₄ and [Pt₂(μ-S)₂(PPh₃)₄TlBr₂][TlBr₄] reveal a greater interaction between the thallium(III) centre and the two sulfide ligands on stepwise replacement of Ph by Br, as indicated by shorter Tl-S and Pt...Tl distances, and an increasing S-Tl-S bond angle. Investigations of the ESI MS fragmentation behaviour of the thallium(III) complexes are reported.application/pdfenThis is an author’s accepted version of an article published in the journal: Inorganica Chimica Acta. ©2009 Elsevier. Used with permission.Platinum complexesthallium complexessulfide ligandscrystal structuresElectrospray mass spectrometryJournal Article10.1016/j.ica.2009.09.045