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Exploiting Ligand Oxidation State



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Exploiting Ligand Oxidation State Cyanometallate Cages with RedoxSwitchable Host Guest Chemistry and Redox Activation of Alkenes by Platinum Complexes with Non innocent Ligands Julie L Boyer Final Seminar August 25 2008 Molecular coordination cages assembled with rigid linkers possess well defined interior cavities The interesting prospect of these ensembles is their capacity to serve as molecular containers to date coordination cages have been exploited as catalysts 1 2 molecular sieves 3 sensors 4 and trapping reagents for reactive species 5 The family of supramolecules discussed herein are constructed from cyanide linkers The rigid frameworks of cyanometallates impart size selective sieving capabilites 6 For example the neutral molecular box CpCo CN 3 4 Cp Ru 4 displays an unparalleled preference for Cs vs K 7 Recent advances in the chemistry of molecular cyanometallates will be addressed with an emphasis on the incorporation of functional subunits into these rigid molecular cages The condensation of the redox addressable Cb Co NCMe 3 PF6 Cb C4Me4 with the tricyanide Cp Rh CN 3 in the presence of alkali metals M generates electroactive cages of the general formula M Cp Rh CN 3 4 Cb Co 4 M Rh4Co4 M K or Cs The analogous homometallic cages M CpCo CN 3 4 Cb Co 4 M Co8 were prepared similarly via the condensation of Cb Co NCMe 3 with CpCo CN 3 in the presence of alkali metal cations The redox addressable Cb CoI subunits of M Co8 cage enabled the tuning of the cyanometallate framework s charge and consequently control of the framework s host guest chemistry Scheme 1 Upon oxidation of M Co8 the encapsulated cation is expelled affording the empty Co8 4 cage The M Co8 cage can be regenerated by the reduction of Co8 4 in the presence of alkali metal cations The electroactive cages displayed voltammetric response for the encapsulated alkali metal cation 8 Cb Co CoCp CpCo CoCb Cb Co CoCp CpCo CoCb 4 FcPF6 4 Cp 2Co Cb Co CoCp CpCo CoCb Cb Co CoCp CpCo CoCb 4 Scheme 1 Redox



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