Oxidation of CH₃NH₂ and (CH₃)₂NH by Ni^III(cyclam)(H₂O)₂³⁺ in Aqueous Solutions

Abstract

NiII (1,4,8,11-

The Redox Chemistry of (N1‐[3‐(2‐aminoethylimino)‐1,1‐dimethylbutyl]ethane‐1,2‐diamine)nickel(II) Perchlorate, NiIIL1(ClO4)2, in Aqueous Solutions –A Pulse Radiolytic and an Electrochemical Study

“…The formation of Ni II L -2H 2+ requires the formation of a C-N double bond, i. e. a significant change in geometry, which is facilitated by the less rigid open ligand. [14] This conclusion is in agreement with the observation that the stabilities of the isomers of Ni III (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraaazacyclotetradecane) differ considerably. [15] …”

Electrocatalytic Oxidation of Amines by Ni­(1,4,8,11‐tetraazacyclotetradecane)2+ Entrapped in Sol–Gel Electrodes

“…The results are similar to the electro-oxidation of these amines on glassy carbon electrodes in the presence of NiL 2+ in solution. [18] Thus, the results demonstrate that NiL 2+ acts as an electrocatalyst also when it is immobilized in sol-gel matrices.…”

“…This choice is based on the following arguments: (1) NiL 2+ is a known electrocatalyst for the oxidation of amines in aqueous solutions [18] and in heterogeneous systems. [19] (2) These amines are formed in a variety of industrial processes as byproducts, [20] that is, as pollutants, and therefore their oxidation is of environmental interest.…”

Reductive nitrosation of methyl amine ligated to a nickel(III) complex

“…However, recently it was shown that Ni(III)(cyclam), Ni III L, oxidizes methyl amine via [14]: [14].) The suggestion that I is a key intermediate in the process prompted us to check whether I, a radical, reacts with NO, a radical, a reaction which will result in the reductive nitrosation of CH 3 NH 2 .…”