Micellar catalysis of the alkylation of mercuric ions by alkyl cobalt(III) complexes. |
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Authors: | R J Allen C A Bunton |
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Affiliation: | 1. CSIRO Oceans and Atmosphere, Underwood Avenue, Floreat, WA 6014, Australia;2. CSIRO Oceans and Atmosphere, Station Street, Aspendale, VIC 3195, Australia;3. CSIRO Oceans and Atmosphere, EcoSciences Precinct, GPO Box 2583, Brisbane, Qld 4001, Australia |
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Abstract: | Anionic micelles of sodium lauryl sulfate, NaLS, catalyze the monoalkylation of Hg2+ in dilute acid by alkyl aquobis-(dimethyl glyoximato) cobalt (III), RCo(DH)2(H2O) degrees and the related propane derivatives RCo(DOH) DOpn (H2O)+, where R = Me, Et, n-C5H11. Nonionic micelles of Igepal do not catalyze the reaction. In the absence of micelles RCo(DH)2(H2O) degrees is considerably more reactive than RCo(DOH)DOpn(H2O)+, but this higher reactivity is offset in part by its higher basicity. Anionic micelles markedly increase the basicity of RCo(DOH)DOpn(H2O)+ and slightly increase that of RCo(DH)2(H2O) degrees. For reactions of the unprotonated Co(III) complexes the maximum rate enhancements by micelles of NaLS are: R = Me, 19(131); Et, 58 (65); n-C5H11, 46 (32). (The values in parentheses are for RCo(DOH)DOpn(H2O)+.) |
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