The reaction chemistry of 2-and 3-aminoalkanethiols with [PtMe3I](4): a new example of the structural diversity of metal thiolates

The reaction of substitution of iodine in [PtMe3I](4) by 2- and 3-aminoalka nethiols, at several metal to ligand ratios and various reaction conditions in organic solvents, proceeds differently depending mainly on the aminoalk anethiol nature. The substitution by 2-diethylaminoethanethiol has led to a partial replacement of iodine affording the complexes [(PtMe3)(4)(mu-I){mu -S(CH2)(2)NEt2}(3)] and [(PtMe3)(3){mu-I,mu-S(CH2)(2)NHEt2}(2)]I. H-1 NMR d ata in solution for the former complex and the X-ray structure of the latte r 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)Me-3(SCH2CH2NMe2)(2)}(2)], as the only product. The X-ray structure of this complex can be described as consisting of two Pt(IV)Me-3(SCH2CH2NM e2)(2) octahedra linked to a naked Pt(II) atom by means of the thiolate sul fur atoms. Consequently, a total substitution of iodine in [PtMe3I](4) toge ther with the reduction of Pt(IV) to Pt(II) have taken place. The reaction of [PtMe3I](4) with the cyclic 3-aminoalkanethiol HSCH(CH2CH2)(2)NMe and wi th the acyclic 3-aminoalkanethiol, HS(CH2)(3)NMe2, afforded the complexes N a[(PtMe3)(2){mu-SCH(CH2CH2),NMe}(3)], [(PtMe3)(2){mu-SCH(CH2CH2)(2)NHMe}(3) ]I-2, and [(PtMe3)(2){mu-S(CH2)(3)NHMe2}(3)]X-2 (X = I or BPh4). They all c onsist of face-shared bioctahedral diplatinum(IV) units of general formula [Me3Pt(mu-SR)(3)PtM3](z), in which the 3-aminothiolates function as bridgin g ligands through their sulfur atoms. Overall, in the case of 3-aminothiols there is a total replacement of iodine, which is accompanied by the disrup tion of the initial cubane structure. (C) 2000 Elsevier Science S.A. All ri ghts reserved.