Redox kinetics as a probe of the supramolecular ...



Title Redox kinetics as a probe of the supramolecular interaction of alpha- and beta-cyclodextrins with amphiphilic nickel(II) complexes of pentaazamacrocycles bearing aliphatic tails
Author(s) Robert I. Haines, J. E. Rowley
Journal Journal of Inclusion Phenomena and Macrocyclic Chemistry
Date 2007
Volume 58
Issue 1-2
Start page 199
End page 204
Abstract Host-guest interactions between alpha- and beta-cyclodextrins and nickel(II) polyazamacrocycles bearing aliphatic pendant arms (n-butyl, n-octyl and n-dodecyl) have been investigated, using redox kinetics as a probe, to estimate binding constants. Electrospray mass spectrometry shows the formation of inclusion complexes in aqueous solution. Cyclic voltammetric measurements show the cyclodextrins to have no effect on the redox potentials for the nickel( II/III) couples. Kinetics of oxidation of the nickel( II) complexes to the tervalent state exhibits rate retardation in the presence of the cyclodextrins. The outer-sphere oxidation of the nickel( II) macrocycles by aqua( 5, 5, 7, 12, 12, 14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-1-acetato) nickel(III), [Ni(hmca)(OH2)](2+) obeys the rate law: Rate = k(obs)[Ni-III(hmca)(OH2)] = [k(2) + k(3)K(CD)][(NiL)-L-II][Ni-III(hmca)(OH2)]/(1 + K-CD[CD]) where k(2) is the rate constant for oxidation of the nickel(II) macrocycle in the absence of cyclodextrins, and k(3) is that for oxidation of the {NiL.CD} inclusion complex.

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