PubMed · 13419147
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R GRASBECK, W NYBERG, K OKUDA. 1957-02-28. [Not Available].. https://pubmed.ncbi.nlm.nih.gov/13419147/
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This commentary concentrates on corrole complexes with the three metal ions that are most relevant to oxidation catalysis: chromium, manganese, and iron. Particular emphasis is devoted to the only recently introduced meso-triarylcorroles and a comparison with the traditionally investigated beta-pyrrole-substituted corroles. Based on a combination of spectroscopic methods, electrochemistry, and X-ray crystallography, it is concluded that in most high-valent metallocorroles the corrole is not oxidized. Both experimental (for (oxo)chromium(V) corrole) and computational (for (oxo)manganese(V) corrole) evidence indicate that the stabilization of high-valent metal ions by corroles originates from a combination of short metal-nitrogen bonds and large metal out-of-plane displacements in the corrole, which lead to quite unexpected interactions of the oxo-metal pi* orbitals with the in-plane orbitals of the corrole.
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This paper describes some of the chemistry of synthetic corrinoids and corphinoids carried out at the ETH (Swiss Federal Institute of Technology) after the completion of the non-enzymic synthesis of vitamin B12 and attempts to delineate the interplay between mechanistic hypotheses, model studies and the experimental research in B12 biosynthesis which had spurred this work. The afterthoughts deal with why and how the work on corrinoids eventually led to an experimental involvement in the problem of a chemical aetiology of the structure of natural nucleic acids.