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“Bioinspired” Metal Complexes of Macrocyclic [N4 2-] and Open Chain [N2O2 2-] Schiff Base Ligands — a Link between Porphyrins and Salicylaldimines

  • Conference paper
Chemistry at the Beginning of the Third Millennium

Abstract

Transition metals play an essential role as active sites of many enzymes. The complex catalytic performance of these biocatalysts should present a continuing challenge to chemists far into the third Millennium. Many attempts have been made in the past decades of the last century to develop new catalysts based on coordination compounds which mimic natural models. Initial success and the first technical applications involved particularly porphyrins and complexes of salicylaldimines. In this paper, we give an overview of chelate complexes of tetradentate Schiff base ligands with either a macrocyclic [N4]2- or an open chain [N2O2]2- donor set derived from aliphatic 3-oxoaldehydes and diamines. These complexes represent a link between those of porphyrin type and those of salicylaldimine type and prove to have many properties and reactions in common with them. The high variability of the complexes’ ligands with regard to the ring size, the extent of the π-electron system, and electronic as well as steric effects of peripheral substituents allow a broad variation of those properties decisive in catalytic performance; such as redox potentials, reactivity of axial coordination sites, and the spin state of the central atom. The redox couples NiII/I as well as the equilibrium constants for the addition of axial ligands to the planar nickel(II) or the penta-coordinated organo-cobalt(III) complexes reflect the high sensitivity of the central atom to electronic effects from equatorial ligands. Some of the macrocyclic nickel complexes are good electrocatalysts for the reduction of carbon dioxide. Most of the discussion focuses on iron complexes, especially their reactivity with different axial ligands, the “push-pull” effects in adducts with mixed axial ligands and some special structural features. First observations of the catalysis of hydroquinone oxidation by an oxidase-like four-electron reduction of dioxygen show that — besides redox potentials, axial reactivity and spin state — the formation of oligonuclear units, stabilized by H-bridges between peripheral oxo-groups and/or axial ligands, seem to play an essential role in catalytic performance. H-bridges are obviously also responsible for the formation of “molecule based magnets” with specific solid-state structures and cooperative magnetic properties.

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  1. Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, August-Bebel-Strasse 2, D-07743, Jena, Germany

    Ernst-G. Jäger

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  1. Department of General Chemistry, University of Pavia, Via Taramelli 12, 27100, Pavia, Italy

    Luigi Fabbrizzi  & Antonio Poggi  & 

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Jäger, EG. (2000). “Bioinspired” Metal Complexes of Macrocyclic [N4 2-] and Open Chain [N2O2 2-] Schiff Base Ligands — a Link between Porphyrins and Salicylaldimines. In: Fabbrizzi, L., Poggi, A. (eds) Chemistry at the Beginning of the Third Millennium. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-04154-3_6

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