Electrochemical Illumination of Intramolecular Communication in Ferrocene-Containing tris-尾-Diketonato Aluminum(III) Complexes; Cytotoxicity of Al(FcCOCHCOCF3)3

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• 作者：Henno J. Gericke ; Alfred J. Muller ; Jannie C. Swarts
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：February 6, 2012
• 年：2012
• 卷：51
• 期：3
• 页码：1552-1561
• 全文大小：547K
• 年卷期：v.51,no.3(February 6, 2012)
• ISSN：1520-510X

文摘

The series of ferrocene-containing tris-尾-diketonato aluminum(III) complexes [Al(FcCOCHCOR)₃] (R = CF₃, 1; CH₃, 2; C₆H₅, 3; and Fc = ferrocenyl = Fe(畏⁵-C₅H₅)(畏⁵-C₅H₄), 4) were synthesized and investigated structurally and electrochemically; complex 1 was subjected to cytotoxicity tests. ¹H NMR-spectroscopy distinguished between the mer and fac isomers of 2 and 3. Complex 1 existed only as the mer isomer. A single crystal X-ray crystallographic determination of the structure of a mer-isomer of Al(FcCOCHCOCF₃)₃, 1, (Z = 4, space group P2₁2₁2₁) demonstrated extensive delocalization of all bonds which explained the pronounced electrochemically observed intramolecular communication between molecular fragments. In contrast to electrochemical studies in CH₂Cl₂/[N(ⁿBu)₄][PF₆], the use of the supporting electrolyte [N(ⁿBu)₄][B(C₆F₅)₄] allowed identification of all Fc/Fc⁺ electrochemical couples by cyclic and square wave voltammetry for 1鈥?b>4. For R = Fc, formal reduction potentials of the six ferrocenyl groups were found to be E掳鈥?= 33, 123, 304, 432, 583, and 741 mV versus free ferrocene respectively. Complex 1 (IC₅₀ = 10.6 渭mol dm^鈥?) was less cytotoxic than the free FcCOCH₂COCF₃ ligand having IC₅₀ = 6.8 渭mol dm^鈥? and approximately 2 orders of magnitude less toxic to human HeLa neoplastic cells than cisplatin (IC₅₀ = 0.19 渭mol dm^鈥?).