Dinuclear platinum(II) sulfide-thiolate complexes [Pt-2(mu-S)(mu-SR)(PPh3)(4)](+) containing fluorinated substituents and the identification of a S center dot center dot center dot C6F5 pi interaction in the crystal structure of [Pt-2(mu-S)(mu-SCH2C6F5)(PPh3)(4)]BPh4 center dot 2C(6)H(6)

作者：Henderson William^*; Saunders Graham C; Hor T S Andy

来源：Inorganica Chimica Acta, 2011, 368(1): 6-12.

DOI：10.1016/j.ica.2010.12.020

• Platinum complexes
• Sulfide complexes
• Thiolate complexes
• Alkylation reactions
• pi Interactions
• Crystal structure

Reactions of the platinum(II) sulfido complex [Pt-2(mu-S)(2)(PPh3)(4)] with the alkyl iodides ICH2CH2(CF2)(n)CF3 (n = 3, 7) gives good yields of the monoalkylated products [Pt-2(mu-S){mu-SCH2CH2(CF2)(n)CF3}(PPh3)(4)](+), which were isolated as PF6- or BPh4- salts, and characterised by ESI mass spectrometry, NMR spectroscopy and elemental analysis. The complex [Pt-2(mu-S){mu-SCH2CH2(CF2)(n)CF3}(PPh3)(4)](+) appears to have normal reactivity for this type of complex, namely reaction with Ph3PAuCl to give [Pt-2(mu-SAuPPh3){mu-SCH2CH2(CF2)(n)CF3}(PPh3)(4)](2+), and reaction with Me2SO4 to give [Pt-2(mu-SMe){mu-SCH2CH2(CF2)(n)CF3}(PPh3)(4)](2+). Reaction of [Pt-2(mu-S)(2)(PPh3)(4)] with C6F5CH2Br gave [Pt-2(mu-S)(mu-SCH2C6F5)(PPh3)(4)](+), isolated as its BPh4- salt, and characterised by NMR spectroscopy and a single-crystal X-ray structure determination. The C6F5 group lies above the {Pt2S2} core of the complex as a result of a S center dot center dot center dot C6F5 p interaction, in contrast to the published structure of [Pt-2(mu-S)(mu-SCH2C6H5)(PPh3)(4)]PF6, where the C6H5 group projects away from the {Pt2S2} core.

• 出版日期2011-3-15