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The novel metallosurfactant Cu(II)-1-tetradecyldiethylenetriamine (Cu(II)TDET) was prepared, and the hydrolyses of 2-acetoxy-5-nitrobenzoic acid (1), 4-acetoxy-3-nitrobenzoic acid (2), 4-nitrophenyl acetate (3), and 2-nitrophenyl acetate (4) in the presence of micellar Cu(II)TDET were examined. The rate of ester hydrolysis for the series followed the order 1 approximately 2>3>4. The larger observed rate (kpsi) for 1 and 2 was attributed to (i) electrostatic interaction between the carboxylate anion and the cationic metallomicelle surface and (ii) the formation of a ternary complex metal:surfactant ligand:substrate (MLnS). The position of the carboxylate anion in the substrate did not significantly affect catalysis. Similar rates were observed when the carboxylate anion was ortho to the acyl ester 1 or para to the reaction center 2. The absence of a significant difference may be associated with the ternary complex coordination geometry, which unfavorably aligned the ligated substrate and the metal-bound hydroxyl. Mixed micellar solutions containing Cu(II)TDET and MTAB or Triton X-100 were examined. Added cosurfactants have a pronounced effect on the catalytic activity of Cu(II)TDET. At a low concentration of Cu(II)TDET the addition of MTAB or Triton X-100 increased the pseudo-first-order rate constant (kpsi) for the hydrolysis of 1 and 3 relative to the rate in pure Cu(II)TDET. The addition of a cosurfactant increased the total micellar volume (VM), promoting substrate incorporation within the pseudophase. At higher metallosurfactant concentration, the rate enhancement was smaller due to the dilution of the substrate within the co-micellar pseudophase.

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The critical micelle concentration of solutions of cetyltrimethylammonium bromide and of tetradecyltrimethylammonium bromides were determined by a kinetic method. This involved the determination of the rates of the hydroxydehalogenation of some activated aromatic substrates over a wide range of detergent concentrations. Measurements were made in solutions containing significant quantities of added hydroxyl ion and substrates which were themselves amphiphilic. Conventional methods cannot be applied with confidence to such systems. The effects of changing hydroxyl ion concentrations, added sodium bromide, changing the nature of the aromatic substrate (whether neutral or charged), the identity of the micellar counterion and the temperature were investigated. It was wound that added bromide or hydroxyl ions resulted in a lower CMC whereas increased temperature led to an increase in the CMC. The nature of the micellar counterion (Br, F, OH, SO4) had little effect on the CMC. The presence of a charged aromatic substrate led to a considerable lowering of the CMC, whereas the neutral aromatic substrate used showed very little effect.

A simple collision theory model for reaction between two different radicals shows that the cross-reaction ratio, @*, is 2 only if the masses and collision diameters of the radicals are identical; for all other combinations of mass and size, @* is greater than 2. The value of d* is shown to depend simply on the ratios of the masses and diameters of the two radicals: which of the two is the heavier or larger is unimportant.Calculated and experimental values of 4* are compared for several systems involving small alkyl and fluoroalkyl radicals, and the relationship between d~* and 6 , the crosscombination ratio, is discussed.