Radiation chemical study of the reaction of Ni+, Co+ and Cd+ with N2O. Evidence for the formation of a hyperoxidised state by oxygen atom transfer

Abstract

Reaction of the hyper-reduced metal ions Ni⁺, Co⁺ and Cd⁺ with N₂O produces N₂ and a hyper-oxidised state M(III) of the metal ion by oxygen atom transfer. When formate is present a chain reaction occurs showing that CO^–₂ reduces M²⁺, and that M(III) reacts with formate ion to produce CO^–₂. Detailed studies of the chain reaction kinetics show that M(III) exists in at least two forms, one probably being a hydrolysis product of the other. With nickel (and probably cadmium) M(III) is not stable and is either chemically similar to the hydroxyl radical or produces it on hydrolysis, e.g., [graphic omitted] With cobalt, a long lived (hours) Co(III) state is formed which may be Co(OH)₃.