ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
(±)-[1-hydro-8H-HDP]cobalt(I) 1Full name of 1: [2,2,3,3,7,7,8,8,12,12,13,13,17,17,18,18,-hexadecamethyl-2,3,7,8,12,13,17,18,-octahydro-1H,23H-10,20-diaza-porphinato]cobalt(I); full name of 2a: dibromo[2,2,3,3,7,7,8,8,12,12,13,13,17,17,18,18-hexadecamethyl-2,3,7,8,12,13,17,18-octahydro-1H,21H-10,20-diazaporphinato]cobalt(III).For the nomenclature of [HDP]-complexes see addendum in [2]. 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.
Additional Material:
11 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19840670718
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