Abstract
The copper(III)-imine-oxime complexes [CuIII(Enio)]+ and [CuIII(Pre)]+ {EnioH2 =N,N∘-ethylene bis(isonitrosoacetylacetoneimine) and PreH2 = N,N∘-propylene bis (isonitrosoacetylacetoneimine)} react very rapidly with iodide. The rate law under fixed conditions for the reaction is given by the equation: −d[CuIII]/dt = (2k2[I−] + 2k3[I−]2)[CuIII] The [CuIII(Enio)]+ reaction was pH-independent whereas the [Cu (Pre)]+ reaction rate increased with increasing pH. Both the k2 and the k3 pathways are believed to involve one-electron transfer. An inner-sphere mechanism may operate in the pathway, first-order in [I−].
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