Abstract
The kinetics of oxidation of 1,4,8,11-tetraazacyclotetradecane-5,7-diamidonickel(II) (‘nickel dioxocyclam’) by peroxodisulfate have been measured in a range of binary aqueous solvent mixtures. Reaction rates are retarded by the presence of organic co-solvents, indicative of destabilization of the transition state (TS) relative to the initial state (IS) in the binary aqueous mixtures. Thus the TS is more hydrophilic than the IS. From solubility measurements of the nickel(II) macrocycle, the transfer chemical potential of the IS of the reaction has been estimated and compared with that of the TS. The transfer potential of the IS is dominated by the solvation of the peroxodisulfate ion.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
B. Sieklucka and D.H. Macartney, Transition Met. Chem., 21, 200 (1996); M.H. Chen, S. Lee, S. Liu and A. Yeh, Inorg. Chem., 35, 2627 (1996); K. Arora, A.P. Bhargava and Y.K. Gupta, J. Chem. Soc., Dalton Trans., 1257 (1990); A. Rodriguez, P. Lopez-Cornejo, P. Perez, F. Muriel, F. Sanchez and J. Burgess, Int. J. Chem. Kinetics, 31, 485 (1999).
H. Eiberberger, S. Steenken, P. O'Neill and D. Schulte-Frohlinde, J. Phys. Chem., 82, 749 (1978).
M.J. Blandamer and J. Burgess, Coord. Chem. Rev., 31, 93 (1980).
R.I. Haines, D.R. Hutchings, R.J. Lucas and D. Miller, Can. J. Chem., 79, 54 (2001).
R.I. Haines and S. Northcott, Can J. Chem., 70, 2785 (1992).
R.I. Haines and Park, J. Coord. Chem., 29, 307 (1993).
R.I. Haines, L. Butt, M.K. Park and D. Wheeler, Can. J. Chem., 71, 976 (1993).
B.R. Bernard, R.I. Haines and J.E. Rowley, Transition Met. Chem., 26, 164 (2001).
L. Fabrizzi, A. Poggi and B. Seghi, Inorg. Synth., 23, 84 (1985).
A. Anichini, L. Fabrizzi and P. Paoletti, Inorg. Chim. Acta, 24, L21 (1977); D.F. Cook and E.D. MacKenzie, Inorg. Chem. Acta, 31, 59 (1978); N.F. Curtis and N.B. Milestone, Aust. J. Chem., 27, 1167 (1974).
R.I. Haines and A. McAuley, Coord. Chem. Rev., 39, 77 (1981).
M.J. Blandamer, J. Burgess and R.I. Haines, J. Inorg. Nucl. Chem., 41, 258 (1979).
S.P. Gavrish and Y.D. Lampeka, J. Coord. Chem., 38, 295 (1996); S.P. Gavrish and Y.D. Lampeka, J. Coord. Chem., 24, 351 (1991).
W.C. Vasudeva and S. Wasif, J. Chem. Soc. (B), 960 (1970).
N.V. Federovich, M.D. Levi, B.B. Damaskin and A.V. Shelpakov, Dokl. Akad. Nauk SSSR, 225, 148 (1975).
M.J. Blandamer and J. Burgess, Coord. Chem. Rev., 31, 93 (1980).
R.I. Haines, D. Pieda and W. Goulding, Transition Met. Chem., (1999).
V. Holba, J. Benko, O. Grancicova and O. Vollarova, Transition Met. Chem., 10, 84 (1985).
V. Holba, O. Grancicova and A. Paulenova, Transition Met. Chem., 12, 121 (1987).
J. Burgess, O. Vollarova and J. Benko, Transition Met. Chem., 12, 238 (1987).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Haines, R.I., Baldwin, R. Initial state versus transition state solvation effects on the kinetics of oxidation of nickel(II) dioxocyclam by peroxodisulfate. Transition Metal Chemistry 27, 284–289 (2002). https://doi.org/10.1023/A:1014888715343
Issue Date:
DOI: https://doi.org/10.1023/A:1014888715343