Dinuclear platinum(II) complexes containing ferrocenylalkyl–thiolate and –selenolate ligands

Alkylation reactions of [Pt2(μ-S)2(PPh3)4] with haloalkylferrocenes FcCH2Cl, Fc(CH2)6Br and Fc(CH2)11Br [Fc = (η5-C5H5)Fe(η5-C5H4)] gave the cationic μ-thiolate complexes [Pt2(μ-S){μ-S(CH2)nFc}(PPh3)4]+ (n = 1, 6, 11), isolated as PF6− and/or BPh4− salts, and characterised by ESI mass spectrometry, NMR spectroscopy, microelemental analysis, and by an X-ray structure determination on [Pt2(μ-S){μ-SCH2Fc}(PPh3)4]PF6. The complex contains the typical folded {Pt2(μ-S)2} core with an axial ferrocenylmethylthiolate ligand. The corresponding selenolate complex [Pt2(μ-Se){μ-SeCH2Fc}(PPh3)4]+ was similarly obtained by alkylation of [Pt2(μ-Se)2(PPh3)4] with FcCH2Cl, and isolated as PF6− and BPh4− salts. The attempted liberation of FcCH2SH from [Pt2(μ-S){μ-SCH2Fc}(PPh3)4]+ using Na2S was not successful.