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- Title
Synthesis, Structure, and Redox Chemistry of a Vitamin-B<sub>12s</sub>-Related Macrocyclic Complex of Cobalt(I).
- Authors
Walder, Lorenz; Rytz, Gerhard; Vögeli, Ulrich; Scheffold, Rolf; Engel, Peter
- Abstract
(±)-[1-hydro-8H-HDP]cobalt(I) 1 is obtained by chemical or electrochemical four-electron reduction of (±)-dibromo- or (±)-dicano[1-hydroxy-8H-HDP]cobalt(III) 2a or 2b4, respectively. The crystal nad molecular structure of 1 was determined by combination of X-ray analysis and MS, 1H-, and 13C-NMR spectroscopy. Square-planar coordinated Co(I) lies closely to the best plane through the four N-atoms which form the first coordination sphere. Thermodynamic data for the coordination of axial bases with the cation of [1-hydroxy-8H-HDP]cobalt 2 in its different metal oxidation states were determined. The pathway of the overall four-electron reduction of 2a to 1 was elucidated: it involves a two-electron reduction of the central metal, a two-electron reduction of the macrocycle accompanied by elimination of the OH-group and final protonation at C(1). Evidence for an intramolecular electron transfer between the central metal and the macrocycle is presented.
- Publication
Helvetica Chimica Acta, 1984, Vol 67, Issue 7, p1801
- ISSN
0018-019X
- Publication type
Academic Journal
- DOI
10.1002/hlca.19840670718