Influence of the terminal ligands on the redox properties of the {Pt <inf>2</inf>(μ-S)<inf>2</inf>} core in [Pt<inf>2</inf>(Ph <inf>2</inf>X(CH<inf>2</inf>)<inf>2</inf>XPh<inf>2</inf>)<inf>2</inf>(μ-S) <inf>2</inf>] (X = P or As) complexes and on their reactivity towards metal centres, protic acids and organic electrophiles

Fernando Novio, Rubén Mas-Ballesté, Iluminada Gallardo, Pilar González-Duarte, Agustí Lledós, Neus Vila

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Abstract

In order to explore possible ways for modulating the unusually rich chemistry shown by complexes of formula [L2Pt(μ-S) 2PtL2] we have studied the influence of the nature of the terminal ligand L on the chemical properties of the {Pt2(μ-S) 2} core. The systematic study we now report allows comparison of the behaviour of [Pt2(dpae)2(μ-S)2] (dpae = Ph2As(CH2)2AsPh2) (1) with the already reported analogue [Pt2(dppe)2(μ-S)2] (dppe = Ph2P(CH2)2PPh2). Complex 1 as well as the corresponding multimetallic derivatives [Pt(dpae){Pt 2(dpae)2(μ-S)2}](BPh4) 2 2, [M{Pt2(dpae)2(μ-S)2} 2]X2 (M = CuII, X = BF4 3; M = ZnII, X = BPh4 4; M = CdII, X = ClO4 5; M = HgII, X = Cl 6 or X2 = Cl1.5[HCl 2]0.5 6′) have been characterized in the solid phase and in solution. Comparison of structural parameters of 1 and 3-6′ with those of the corresponding phosphine analogues, together with the results of the electrochemical study for 1, allow us to conclude that replacement of dppe by dpae causes a decrease in basicity of the {Pt2(μ-S)2} core. The study of the reactivity of 1 towards CH2Cl2 and protic acids has led to the structural characterization of [Pt(dpae)(S 2CH2)] 9 and [PtCl2(dpae)] 10. Moreover, comparison with the reactivity of [Pt2(dppe)2(μ-S) 2] indicates that the stability of the intermediate species as well as the nature of the final products in both multistep reactions are sensitive to the nature of the terminal ligand. © The Royal Society of Chemistry 2005.
Original languageEnglish
Pages (from-to)2742-2753
JournalDalton Transactions
Issue number16
DOIs
Publication statusPublished - 21 Aug 2005

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