Extending knowledge on the nucleophilicity of the {Pt<inf>2</inf>S<inf>2</inf>} core: Ph<inf>2</inf>PCH<inf>2</inf>CH<inf>2</inf>PPh<inf>2</inf> as an alternative terminal ligand in [L<inf>2</inf>Pt(μ-S)<inf>2</inf>PtL<inf>2</inf>] metalloligands

Mercè Capdevila, Yolanda Carrasco, William Clegg, Robert A. Coxall, Pilar González-Duarte, Agustí Lledós, José Antonio Ramírez

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45 Citations (Scopus)

Abstract

The reaction of [Pt2(dppe)2(μ-S)2] 1, with metal complexes or metal salts gave different types of complexes depending on the nature of the heterometal and of the stoichiometric ratios employed. Thus, a trinuclear complex of formula [Pt(dppe){Pt2(dppe)2(μ3-S) 2}]Cl2 2 and an apparently mixed PdxPt3-x product 3 have been prepared and characterised. Alternatively, dissolution of 1 in chlorinated solvents affords 2 easily and 3 is formed from 1 with [PdCl2(dppe)]. The pentanuclear complexes of formula [M{Pt2(dppe)2(μ3-S)2}2]X 2 (M = Zn 4 or Cd 5, X = ClO4; M = Cd, X2 = [CdCl4] 5′; M = Hg, X2 = [PF6][HgCl4]0.5 6) have been obtained. The structures of complexes 2, 3, 4, 5, 5′ and 6 have been determined crystallographically. Complex 2 comprises three slightly distorted square-planar cis-PtP2S2 co-ordination planes sharing two μ3-S ligands. X-Ray data and NMR studies in solution of different crops of crystals support that 3 is essentially a simple solid-solution mixture of pure complexes [Pd(dppe){Pt2(dppe)2(μ3-S) 2}][BPh4]2 3′ and [Pt(dppe)-{Pd2(dppe)2(μ3-S) 2}][BPh4]2 3″ in variable proportions with at most a minor component of the homometallic complex 2. The structure of the cations of complexes 4, 5, 5′ and 6 comprises two {Pt2S2} butterflies linked through sulfur to the metal(II) ion, which shows a significantly distorted tetrahedral environment. All complexes have been fully characterised by multinuclear NMR techniques and the corresponding parameters are reported.
Original languageEnglish
Pages (from-to)3103-3113
JournalJournal of the Chemical Society - Dalton Transactions
Issue number17
DOIs
Publication statusPublished - 7 Sep 1999

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