Reaction of arylhydroxylamines with [Pd(Neoc)(NO3)2] (Neoc = neocuproine) : Non-innocent behavior of the nitrate anion
Articolo
Data di Pubblicazione:
2018
Citazione:
Reaction of arylhydroxylamines with [Pd(Neoc)(NO3)2] (Neoc = neocuproine) : Non-innocent behavior of the nitrate anion / F. Ferretti, M. Rimoldi, F. Ragaini, P. Macchi. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - 470(2018 Jan 30), pp. 284-289. [10.1016/j.ica.2017.05.014]
Abstract:
In an effort to understand the first stages of the reduction of nitroarenes to anilines by palladium/phenanthroline complexes and suspecting that arylhydroxylaminato complexes may be intermediates in this process, we investigated the reactivity of [Pd(Neoc)(NO3)(2)] (Neoc = neocuproine = 2,9-dimethyl-1,10-phenanthroline) with 3,5-dichlorophenylhydroxylamine. Spectroscopic evidence indicates that the desired [Pd(Neoc)(ONHC6H3Cl2)(NO3)] is indeed formed, but the complex is not stable and decomposes within a few hours. Two of the decomposition products were characterized by single crystal X-ray diffraction. They are a N-aryl-N-nitrosohydroxylaminato complex, [Pd(Neoc)(ON(3,5-C6H3Cl2) NO)][NO3] (major decomposition product) and a nitro-nitrate complex [Pd(Neoc)(NO2)(NO3)]. The results indicate that the nitrate ion is not innocent in the starting complex and oxidize hydroxylamine, being reduced itself to NO2 and NO.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
arylhydroxylamines; nitrate; nitroarenes; palladium; phenanthroline; physical and theoretical chemistry; inorganic chemistry; materials chemistry2506 metals and alloys
Elenco autori:
F. Ferretti, M. Rimoldi, F. Ragaini, P. Macchi
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