The reaction chemistry of 2- and 3-aminoalkanethiols with [PtMe<inf>3</inf>I]<inf>4</inf>: A new example of the structural diversity of metal thiolates

Núria Duran, William Clegg, Kelly A. Fraser, Pilar González-Duarte

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The reaction of substitution of iodine in [PtMe3I]4 by 2- and 3-Aminoalkanethiols, at several metal to ligand ratios and various reaction conditions in organic solvents, proceeds differently depending mainly on the aminoalkanethiol nature. The substitution by 2-Diethylaminoethanethiol has led to a partial replacement of iodine affording the complexes [(PtMe3)4(μ-I){μ-S(CH2)2NEt2}3] and [(PtMe3)3{μ-I,μ-S(CH2)2NHEt2}2]I. 1H NMR data in solution for the former complex and the X-Ray structure of the latter show that both are structurally related to the initial [PtMe3I]4 cubane. The replacement of iodine by 2-Dimethylaminoethanethiol has led to [Pt(II){Pt(IV)Me3(SCH2CH2NMe2)2}2], as the only product. The X-Ray structure of this complex can be described as consisting of two Pt(IV)Me3(SCH2CH2NMe2)2 octahedra linked to a naked Pt(II) atom by means of the thiolate sulfur atoms. Consequently, a total substitution of iodine in [PtMe3I]4 together with the reduction of Pt(IV) to Pt(II) have taken place. The reaction of [PtMe3I]4 with the cyclic 3-Aminoalkanethiol HSCH(CH2CH2)2NMe and with the acyclic 3-Aminoalkanethiol, HS(CH2)3NMe2, afforded the complexes Na[(PtMe3)2{μ-SCH(CH2CH2)2NMe}3], [(PtMe3)2{μ-SCH(CH2CH2)2NHMe}3]I2 and [(PtMe3)2{μ-S(CH2)3NHMe2}3]X2 (X = I or BPh4). They all consist of face-Shared bioctahedral diplatinum(IV) units of general formula [Me3Pt(μ-SR)3PtMe3](z), in which the 3-Aminothiolates function as bridging ligands through their sulfur atoms. Overall, in the case of 3-Aminothiols there is a total replacement of iodine, which is accompanied by the disruption of the initial cubane structure. (C) 2000 Elsevier Science S.A.
Original languageEnglish
Pages (from-to)790-799
JournalInorganica Chimica Acta
Publication statusPublished - 30 Apr 2000


  • Aminothiolato complexes
  • Crystal structures
  • Platinum complexes
  • Thiolato complexes


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