Oxidation of cobalt(ii) bispidine complexes with dioxygen*
Bispidine (3,7-diazabicyclo[3.3.1]nonane) ligands, derivatives of diazaadamantane, possess a very rigid backbone and have a high degree of pre-organization for cis-octahedral coordination geometries. Despite their rigidity, they exert a flexible coordination sphere, resulting in stable complexes wit...
Gespeichert in:
| Hauptverfasser: | , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
10 February 2017
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| In: |
Australian journal of chemistry
Year: 2017, Jahrgang: 70, Heft: 5, Pages: 576-580 |
| ISSN: | 1445-0038 |
| DOI: | 10.1071/CH16674 |
| Online-Zugang: | Verlag, Volltext: http://dx.doi.org/10.1071/CH16674 Verlag, Volltext: http://www.publish.csiro.au/ch/CH16674 
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| Verfasserangaben: | Peter Comba, Bianca Pokrandt and Hubert Wadepohl |
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| 520 | |a Bispidine (3,7-diazabicyclo[3.3.1]nonane) ligands, derivatives of diazaadamantane, possess a very rigid backbone and have a high degree of pre-organization for cis-octahedral coordination geometries. Despite their rigidity, they exert a flexible coordination sphere, resulting in stable complexes with a variety of metal ions in various oxidation states. Due to the known high III/II redox potentials of their cobalt complexes, the CoII bispidine complexes are generally resistant to oxidation by dioxygen. Discussed in the present study are various CoII bispidine complexes with tetra- and pentadentate bispidines, with one of these complexes shown to be unstable under aerobic conditions. The decay process has been identified as an oxidative elimination of the 2-methylene pyridine substituent at one of the tertiary amine donors, resulting in picolinate, which is found coordinated to a CoIII product, where the dealkylated N-donor remains unprotonated. The mechanism of this interesting reaction has been studied, and details of the resulting structure of the product complex are discussed. | ||
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