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Title: Thallium(III) complexes of the metalloligands [Pt2(μ-S)2(PPh3)4] and [Pt2(μ-Se)2(PPh3)4]
Authors: Rose, S.L.
Henderson, W.
Nicholson, B.K.
Hor, T.S.A. 
Keywords: Crystal structures
Electrospray mass spectrometry
Platinum complexes
Sulfide ligands
Thallium complexes
Issue Date: 1-Dec-2009
Citation: Rose, S.L., Henderson, W., Nicholson, B.K., Hor, T.S.A. (2009-12-01). 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. ScholarBank@NUS Repository.
Abstract: Reactions 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. © 2009 Elsevier B.V. All rights reserved.
Source Title: Inorganica Chimica Acta
ISSN: 00201693
DOI: 10.1016/j.ica.2009.09.045
Appears in Collections:Staff Publications

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