The outer-sphere association of p-sulfonatothiacalix[4]arene with some Co(III) complexes: the effect on their redox activity in aqueous solutions |
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| Authors: | A R Mustafina V G Shtyrlin L Ya Zakharova V V Skripacheva R R Zairov S E Solov’eva I S Antipin A I Konovalov |
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| Institution: | (1) A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences, Arbuzov str. 8, Kazan, 420088, Russia;(2) A.M. Butlerov Chemistry Institute, Kazan State University, Kremlyovskaya Str., 18, 420008 Kazan, Russia |
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| Abstract: | The effect of the ion-pairing of Co(III) complexes with p-sulfonatothiacalix4]arene (STCA) on Fe(II)–Co(III) electron transfer rate was evaluated from the analysis and comparison of kinetic data in double Co(III)–Fe(II)
and triple Co(III)–Fe(II)—STCA systems at various concentration conditions. Complexes Co(en)3]3+(1), Co(en)2ox]+(2), Co(dipy)3]3+ (3), Co(His)2]+(4) and Fe(CN)6]4− were chosen as Co(III) and Fe(II) compounds. The effect of STCA was found to correlate with the association mode. The outer-sphere association with STCA was found to exhibit the insignificant effect on Fe(II)–Co(III) electron transfer k
et constants for complexes 3 and 4 with bulky and rigid chelate rings, while more sufficient inclusion of flexible ethylendiaminate rings of 1 and 2 into the cavity of STCA results in the unusual increase of k
et. |
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| Keywords: | Co(III) complex Inclusion complex Outer-sphere electron transfer p-sulfonatothiacalix[4]arene |
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