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Issue 12, 1999
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Cycloplatinated ferrocenylamine-carboxylate and dithiocarbamate complexes: synthesis and aqueous properties

Kim McGrouther,  Debbrah K. Weston,  Delwyn Fenby,  Brian H. Robinson  and  Jim Simpson 

Abstract

Metathetical reaction of the cyclometallated ferrocenylamine complexes [Pt{FeCp(σ,η5-C5H3CHRNMe2)}(dmso)Cl] (R = H 1 or Me 3) and [Pt2{Fe(σ,η5-C5H3CH2NMe2)2}(dmso)2Cl2] 2 with TlX (X = OAc or malonate), or the direct reaction with P(C6H4SO3-m)33– (tppms) and Et2NCS2–(dedtc), gave [Pt{FeCp(σ,η5-C5H3CHRNMe2)}(dmso)(OAc)], [{Pt[FeCp(σ,η5-C5H3CHRNMe2)](dmso)}2(mal)] (mal = malonate), Na5[Pt{FeCp(σ,η5-C5H3CHRNMe2)}(tppms)2], [Pt{FeCp(σ,η5-C5H3CHRNMe2)}(dedtc)] and bis-Pt analogues. These complexes were characterised by analysis, ES-MS and 1H, 13C and 195Pt NMR. Metathetical reaction of 1–3 with silver(I) salts generally gave ferrocenium derivatives. Substitution trans to the Pt–N or Pt–C bond is determined by the acceptor character of the co-ordinating group and this together with steric constraints limit the range of carboxylato complexes. The acetato complex [Pt{FeCp(σ,η5-C5H3CH2NMe2)}(dmso)(OAc)] crystallises with one molecule of H2O and a single crystal structure indicates a hydrogen bond between a solvent H2O and acetate ligand. Aqueous solutions of the water-soluble OAc, malonate and tppms complexes were studied by electrochemical and spectroscopic techniques. Their chemistry is regulated by pH-dependent equilibria involving aqua and hydroxo complexes and competing oxidation to the ferrocenium compound by molecular oxygen.

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Article type: Paper
DOI: 10.1039/A901260E
Citation: J. Chem. Soc., Dalton Trans., 1999,0, 1957-1966
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    Cycloplatinated ferrocenylamine-carboxylate and dithiocarbamate complexes: synthesis and aqueous properties

    K. McGrouther, D. K. Weston, D. Fenby, B. H. Robinson and J. Simpson, J. Chem. Soc., Dalton Trans., 1999, 0, 1957
    DOI: 10.1039/A901260E

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