Photolysis of aqueous [Os(NH3)5(N2)]2+: Dismutation of coordinated dinitrogen

Dinitrogen ligand undergoes a photodismutation. [Display omitted] ► Upon MLCT excitation (λirr=254nm) aqueous [OsII(NH3)5(N2)]2+ undergoes a photolysis. ► Photolysis: [Os(NH3)5(N2)]2++O2→[Os(NH3)4N]3++NO2-+NH3. ► The N2-ligand undergoes a dismutation to nitride and nitrite. Aqueous [OsII(NH3)5(N2)]2...

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Bibliographic Details
Published in:Inorganica Chimica Acta 2012-08, Vol.391, p.229-231
Main Authors: Kunkely, Horst, Vogler, Arnd
Format: Article
Language:English
Subjects:
Coordination chemistry
Dinitrogen
Osmium
Photochemistry
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Summary:Dinitrogen ligand undergoes a photodismutation. [Display omitted] ► Upon MLCT excitation (λirr=254nm) aqueous [OsII(NH3)5(N2)]2+ undergoes a photolysis. ► Photolysis: [Os(NH3)5(N2)]2++O2→[Os(NH3)4N]3++NO2-+NH3. ► The N2-ligand undergoes a dismutation to nitride and nitrite. Aqueous [OsII(NH3)5(N2)]2+ undergoes a photolysis with UV light (λirr=254nm). The main photoreaction proceeds according to the equation: [OsII(NH3)5(N2)]2++O2→[OsVI(NH3)4N]3++NO2-+NH3. The photolysis can thus be viewed as photodismutation of the coordinated N2 ligand yielding N−III (nitride) and N+III (nitrite). This reaction is coupled with an additional redox process: (OsII+O2→OsVI+2O2−).
ISSN:0020-1693
1873-3255
DOI:10.1016/j.ica.2012.04.021