Issue 18, 2018

The photochemical generation of superoxide Rh(iii) complexes

Abstract

The photolysis products of the [Rh(NH3)5(NO2)](NO3)2 complex in aqueous solutions were studied by electron paramagnetic resonance (EPR), UV-visible (UV-vis), and 15N nuclear magnetic resonance (15N NMR) spectroscopies. Aqueous solutions of [Rh(NH3)5(NO2)](NO3)2 became blue when exposed to UV irradiation under an oxygen-containing atmosphere while aqueous solutions of [Rh(NH3)5(NO2)](NO3)2 with additives of NaNO2 turned orange under the same conditions. Photolysis of degassed [Rh(NH3)5(NO2)](NO3)2 solutions did not lead to any change of their color. It was suggested that, as a result of the photolysis, the complex decomposed with the formation of a NO2 fragment and a fragment containing Rh(II). In the presence of molecular oxygen in solution, a superoxide complex, [Rh(NH3)5O2]2+, was formed, in which electron transfer from the metal ion to O2 took place.

Graphical abstract: The photochemical generation of superoxide Rh(iii) complexes

Article information

Article type
Paper
Submitted
24 May 2018
Accepted
07 Aug 2018
First published
21 Aug 2018

New J. Chem., 2018,42, 15231-15236

The photochemical generation of superoxide Rh(III) complexes

V. Nadolinny, A. Belyaev, A. Komarovskikh, S. Tkachev and I. Yushina, New J. Chem., 2018, 42, 15231 DOI: 10.1039/C8NJ02570C

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