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Extending knowledge on the nucleophilicity of the {Pt2S2} core: Ph2PCH2CH2PPh2 as an alternative terminal ligand in [L2Pt(μ-S)2PtL2] metalloligands

Lookup NU author(s): Professor William Clegg

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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.

Publication metadata

Author(s): Capdevila M, Carrasco Y, Clegg W, Coxall RA, Gonzalez-Duarte P, Lledos A, Ramirez JA

Publication type: Article

Publication status: Published

Journal: Journal of the Chemical Society - Dalton Transactions

Year: 1999

Issue: 17

Pages: 3103-3113

Print publication date: 07/09/1999

ISSN (print): 0300-9246

ISSN (electronic): 1364-5447

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/A903899J

DOI: 10.1039/a903899j

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