Abstract
For the past three years, we have been in pursuit of the redox properties of various pentacoordinate metalloporphyrins which remain coordinated to the same axial ligand upon electron transfer. Porphyrins with a high degree of steric hindrance built onto only one side of the porphyrin seemingly provide a straightforward means for preparing pentacoordinate metalloporphyrin complexes. However, ligand addition studies on the “picket fence”, “strapped”, “pocket” and “bis-pocket” porphyrins have indicated that these materials are unsuitable for this type of study because diadduct formation can occur1–4. Likewise, the various “strapped” metalloporphyrins are not appropriate because of the accessibility of the metal centers to coordination by components of the supporting electrolyte. Metallo derivatives of Baldwin’s “capped” porphyrin5 have been selected (see Figure 1 for the structure of the Mn derivative). We have shown that the presence of the pyrromellitoyl cap impeded formation of Co capped porphyrin-nitrogenous base diadducts, even when a very strong thermodynamic driving force for formation of a hexacoordinate metal center was present6.
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Bottomley, L.A., Luck, J.F., Neely, F.L., Quick, J.S. (1988). Redox Reactivity of Manganese “Capped” Metalloporphyrins. In: Dryhurst, G., Niki, K. (eds) Redox Chemistry and Interfacial Behavior of Biological Molecules. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-9534-2_5
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DOI: https://doi.org/10.1007/978-1-4615-9534-2_5
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