Crown ethers solution behaviour

The oxidative behaviour of glycolaldehyde towards hexacyanoferrate(III) in alkaline media has been investigated and a mechanism proposed, which involves an intermediate alkoxide ion. Reactions of tetranitromethane with the luminol and luminol-peroxide radical anions have been shown to contribute substantially to the tetranitromethane reduction in luminol oxidation with hexacyanoferrate(III) in aerated aqueous alkali solutions. The retarding effect of crown ethers on the oxidation of triethylamine by hexacyanoferrate(III) ion has been noted. The influence of ionic strength on the rate constant of oxidation of ascorbic acid by hexacyanofer-rate(III) in acidic media has been investigated. The oxidations of CH2=CHX (where X = CN, CONH2, and C02 ) by alkaline hexacyanoferrate(III) to diols have been studied. ... 

Costero. A.M. Monrabal. E. Andreu, C. Martmez-Manez. R. Soto, J. Padilla-Tosta, M. Pardo, T. Ochando. L.E. Amigo, J.M. Synthesis, solution and electrochemical behaviour of new aza-crown ethers derived from biphenyl. J. Chem. Soc., Dalton Trans. 2000. 361-367. 

CR represent different conformations of the crown ether. T1+ is closer to Ag+ than to K+ or Rb+ in its behaviour. In studies of the aquation of [RhCl,] " by Hg +, Tl +, Cd +, and In + and of the equation of [RhBre] " by Tl + there is a general correlation between the rate and the stability constant of the monohalogeno-complex of the catalytic cation. The decomposition of [MeTl(OAc)2] to TlOAc and MeCOaOMe has been studied in a variety of solvents. Usually simple first-order kinetics are observed, but in deuteuriochloroform and in THE there is an initial induction period in which the solution becomes saturated with TlOAc. The authors propose a rate-determining 5n2 reaction of [AcO] with the methyl group bonded to thallium. 

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