Abstract
In the octahedral cobalt(III) system, the most widely studied reactions in aqueous solutions are the solvolytic aquation and the base hydrolysis. Both reactions have been shown to take place by a rearrangement, either SN1 or SN2, between the solvation shell and the coordination shell of the complexes (1, 2). The dependence of the rates of solvolytic aquation of complexes of the type [Co en2 A Cl] n+ (where en = ethylenediamine and A = a variable orientingligand) on the nature of A has led to the postulation of a duality of mechanism for the process (3, 4). Electron-repelling groups facilitate dissociation of the chlorine ligand and give rise to a unimolecular mechanism, while electron-attracting groups assist a bimolecular reaction. For the base hydrolysis of these cations, the assignment of mechanism has been contro - versial. BASOLO and PEARSON ( 5) suggested that an SN1CB mechanism operates involving a pre -equilibrium in which the hydroxide ion removes a proton from one of the amine nitrogens forming an amido conjugate base which then undergoes a rate -determining dissociation of the chloride ion. BROWN, INGOLD and NYHOLM (6) however preferred an SN2 mechanism in which the hydroxide ion directly replaces the chlorine ligand.
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References
INGOLD, NYHOLM and TOBE, Nature, 187, 477 (1960).
CHAN and TOBE, J. Chem. Soc. (London), 1962, 4531.
ASPERGER and INGOLD, J. Chem. Soc. (London), 1956, 2862.
BASOLO and PEARSON, “Mechanism of Inorganic Reactions”, John Wiley and Sons, Inc., New York, p. 166 (1958).
BASOLO and PEARSON, reference (4), p.124.
BROWN, INGOLD and NYHOLM, J. Chem. Soc. (London), 1953, 2674.
S BALDWIN, J. Chem. Soc. (London), 1960, 4369.
NYHOLM and TOBE, J. Chem. Soc. (London), 1956, 1707.
CATON and PRUE, J. Chem. Soc. (London), 1956, 671.
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Chan, S.C., Leh, F. (1964). The Aquation and Base Hydrolysis of Chlorobis(Ethylenediamine)Cobalt(III) Cations Containing Ammonia Derivatives as Orienting Ligands. In: Gutmann, V. (eds) Proceedings of the 8th International Conference on Coordination Chemistry. Springer, Vienna. https://doi.org/10.1007/978-3-7091-3650-8_114
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DOI: https://doi.org/10.1007/978-3-7091-3650-8_114
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