Electrochemical illumination of intramolecular communication in ferrocene-containing tris -β-diketonato aluminum(III) complexes; Cytotoxicity of Al(FcCOCHCOCF 3) 3

Henno J. Gericke; Alfred J. Muller; Jannie C. Swarts

doi:10.1021/ic201849u

Electrochemical illumination of intramolecular communication in ferrocene-containing tris -β-diketonato aluminum(III) complexes; Cytotoxicity of Al(FcCOCHCOCF ₃) ₃

Henno J. Gericke, Alfred J. Muller, Jannie C. Swarts

Chemical Sciences

University of The Free State

Research output: Contribution to journal › Article › peer-review

27 Citations (Scopus)

Abstract

The series of ferrocene-containing tris-β-diketonato aluminum(III) complexes [Al(FcCOCHCOR) ₃] (R = CF ₃, 1; CH ₃, 2; C ₆H ₅, 3; and Fc = ferrocenyl = Fe(η ⁵- C ₅H ₅)(η ⁵-C ₅H ₄), 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(FcCOCHCOCF ₃) ₃, 1, (Z = 4, space group P2 ₁2 ₁2 ₁) demonstrated extensive delocalization of all bonds which explained the pronounced electrochemically observed intramolecular communication between molecular fragments. In contrast to electrochemical studies in CH ₂Cl ₂/[N( ⁿBu) ₄][PF ₆], the use of the supporting electrolyte [N( ⁿBu) ₄][B(C ₆F ₅) ₄] allowed identification of all Fc/Fc ⁺ electrochemical couples by cyclic and square wave voltammetry for 1-4. For R = Fc, formal reduction potentials of the six ferrocenyl groups were found to be E°′ = 33, 123, 304, 432, 583, and 741 mV versus free ferrocene respectively. Complex 1 (IC ₅₀ = 10.6 μmol dm ^-3) was less cytotoxic than the free FcCOCH ₂COCF ₃ ligand having IC ₅₀ = 6.8 μmol dm ^-3 and approximately 2 orders of magnitude less toxic to human HeLa neoplastic cells than cisplatin (IC ₅₀ = 0.19 μmol dm ^-3).

Original language	English
Pages (from-to)	1552-1561
Number of pages	10
Journal	Inorganic Chemistry
Volume	51
Issue number	3
DOIs	https://doi.org/10.1021/ic201849u
Publication status	Published - 6 Feb 2012

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{c5e9c55721794dd09f833f18a6e3d436,

title = "Electrochemical illumination of intramolecular communication in ferrocene-containing tris -β-diketonato aluminum(III) complexes; Cytotoxicity of Al(FcCOCHCOCF 3) 3 ",

abstract = "The series of ferrocene-containing tris-β-diketonato aluminum(III) complexes [Al(FcCOCHCOR) 3] (R = CF 3, 1; CH 3, 2; C 6H 5, 3; and Fc = ferrocenyl = Fe(η 5- C 5H 5)(η 5-C 5H 4), 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(FcCOCHCOCF 3) 3, 1, (Z = 4, space group P2 12 12 1) demonstrated extensive delocalization of all bonds which explained the pronounced electrochemically observed intramolecular communication between molecular fragments. In contrast to electrochemical studies in CH 2Cl 2/[N( nBu) 4][PF 6], the use of the supporting electrolyte [N( nBu) 4][B(C 6F 5) 4] allowed identification of all Fc/Fc + electrochemical couples by cyclic and square wave voltammetry for 1-4. For R = Fc, formal reduction potentials of the six ferrocenyl groups were found to be E°′ = 33, 123, 304, 432, 583, and 741 mV versus free ferrocene respectively. Complex 1 (IC 50 = 10.6 μmol dm -3) was less cytotoxic than the free FcCOCH 2COCF 3 ligand having IC 50 = 6.8 μmol dm -3 and approximately 2 orders of magnitude less toxic to human HeLa neoplastic cells than cisplatin (IC 50 = 0.19 μmol dm -3).",

author = "Gericke, {Henno J.} and Muller, {Alfred J.} and Swarts, {Jannie C.}",

year = "2012",

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T1 - Electrochemical illumination of intramolecular communication in ferrocene-containing tris -β-diketonato aluminum(III) complexes; Cytotoxicity of Al(FcCOCHCOCF 3) 3

AU - Gericke, Henno J.

AU - Muller, Alfred J.

AU - Swarts, Jannie C.

PY - 2012/2/6

Y1 - 2012/2/6

N2 - The series of ferrocene-containing tris-β-diketonato aluminum(III) complexes [Al(FcCOCHCOR) 3] (R = CF 3, 1; CH 3, 2; C 6H 5, 3; and Fc = ferrocenyl = Fe(η 5- C 5H 5)(η 5-C 5H 4), 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(FcCOCHCOCF 3) 3, 1, (Z = 4, space group P2 12 12 1) demonstrated extensive delocalization of all bonds which explained the pronounced electrochemically observed intramolecular communication between molecular fragments. In contrast to electrochemical studies in CH 2Cl 2/[N( nBu) 4][PF 6], the use of the supporting electrolyte [N( nBu) 4][B(C 6F 5) 4] allowed identification of all Fc/Fc + electrochemical couples by cyclic and square wave voltammetry for 1-4. For R = Fc, formal reduction potentials of the six ferrocenyl groups were found to be E°′ = 33, 123, 304, 432, 583, and 741 mV versus free ferrocene respectively. Complex 1 (IC 50 = 10.6 μmol dm -3) was less cytotoxic than the free FcCOCH 2COCF 3 ligand having IC 50 = 6.8 μmol dm -3 and approximately 2 orders of magnitude less toxic to human HeLa neoplastic cells than cisplatin (IC 50 = 0.19 μmol dm -3).

AB - The series of ferrocene-containing tris-β-diketonato aluminum(III) complexes [Al(FcCOCHCOR) 3] (R = CF 3, 1; CH 3, 2; C 6H 5, 3; and Fc = ferrocenyl = Fe(η 5- C 5H 5)(η 5-C 5H 4), 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(FcCOCHCOCF 3) 3, 1, (Z = 4, space group P2 12 12 1) demonstrated extensive delocalization of all bonds which explained the pronounced electrochemically observed intramolecular communication between molecular fragments. In contrast to electrochemical studies in CH 2Cl 2/[N( nBu) 4][PF 6], the use of the supporting electrolyte [N( nBu) 4][B(C 6F 5) 4] allowed identification of all Fc/Fc + electrochemical couples by cyclic and square wave voltammetry for 1-4. For R = Fc, formal reduction potentials of the six ferrocenyl groups were found to be E°′ = 33, 123, 304, 432, 583, and 741 mV versus free ferrocene respectively. Complex 1 (IC 50 = 10.6 μmol dm -3) was less cytotoxic than the free FcCOCH 2COCF 3 ligand having IC 50 = 6.8 μmol dm -3 and approximately 2 orders of magnitude less toxic to human HeLa neoplastic cells than cisplatin (IC 50 = 0.19 μmol dm -3).

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -

Electrochemical illumination of intramolecular communication in ferrocene-containing tris -β-diketonato aluminum(III) complexes; Cytotoxicity of Al(FcCOCHCOCF ₃) ₃

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