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Complexation between ferrocene-based 2,2′-bipyridine ligands and copper(I) cations

Lookup NU author(s): Emeritus Professor Anthony Harriman


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Copper(I) cations bind to a ferrocene-based ligand bearing two pendant 2,2′-bipyridine groups to form three distinct complexes possessing compositions of 1:1, 1:2 and 2:2 (metal to ligand), respectively. The 2:2 complex exists in the form of a double-stranded metallo-helicate but it is unstable in solution with respect to dissociation into the mononuclear species. Stability constants have been determined for each of the complexes using UV-visible spectrophotometric titrations. With this information, together with data derived from competitive complexation studies, electrospray mass spectrometry and electrochemistry, the mechanism by which the metallo-helicate self assembles in solution has been deduced. It is clear that the binuclear complex forms on dimerization of the 1:1 complex, for which there is only a small thermodynamic driving force (ΔG0 = -3.5 kJ mol-1).

Publication metadata

Author(s): Harriman A, Ziessel R, Moutet J-C, Saint-Aman E

Publication type: Article

Publication status: Published

Journal: Physical Chemistry Chemical Physics

Year: 2003

Volume: 5

Issue: 8

Pages: 1593-1598

ISSN (print): 1463-9076

ISSN (electronic): 1463-9084

Publisher: Royal Society of Chemistry


DOI: 10.1039/b210591h


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