Radiation synthesis of iron(II) and ruthenium(II) alkylnitroso complexes

The radiolysis of deoxygenated aqueous solutions of Ru(NH3)5NO3+ and Fe(CN)5NO2- in the presence of organic compounds (RH) generates alkylnitroso complexes of the form Ru(NH3)5N(O)R2+ and Fe(CN)5N(O)R3- where RH = tert-butyl alcohol, tert-butyl amine, N,N-dimethylacetamide, α-aminoisobutyric acid, pivalic acid, and α-hydroxyisobutyric acid. The products form from the rapid combination of the β-carbon radical derived from the reaction of the organic compound with OH radicals and the one-electron reduced metal complex formed by interaction with e-sub(aq). The alkylnitroso complexes are moderately O2-insensitive but display varying degrees of thermal stability. Stability permitting, these complexes have been characterized by ion-exchange chromatography and UV-vis-IR spectroscopy. The green ruthenium complexes exhibit lambdasub(max) 740 and 342 nm and νsub(NO) in the 1365 to 1405 cm-1 region. The less stable red iron analogues absorb at 475 and approximately 250 nm. (author)