NDLI: Correlation analysis of reactivity in the reduction of Co(en)2Br2+ by Fe(CN)64– in water

Content Provider	Springer Nature Link
Author	Poonkodi, Selvanayagam P. R. Anbalagan, Krishnamoorthy
Copyright Year	2001
Abstract	The reduction of [Co(en)$_{2}$Br$_{2}$]$^{+}$ by [Fe(CN)$_{6}$]$^{4−}$ in H$_{2}$O–MeOH and H$_{2}$O–1,4-dioxane mixtures has been studied over a range of solvent compositions [5–30% (v/v)]. The reduction of [Co(en)$_{2}$Br$_{2}$]$^{+}$ was monitored under second order conditions and was found to be rapid in the various solvent compositions investigated. The favoured mechanism is an outer-sphere electron-transfer process consisting of elementary steps, ion-pair formation (K $_{IP}$), electron-transfer (k $_{et}$) and successor dissociation. Therefore, the overall rate constant, k $_{2}$ = K $_{IP}$ k $_{et}$[Co(en)$_{2}$- Br$_{2}$ $^{+}$][Fe(CN)$_{6}$ $^{4−}$]. The rates increase as the proportion of organic cosolvent increases. The rates correlate with solvent properties, such as relative permittivity (ε$_{r}$) and the Grunwald–Winstein parameter, Y $_{GW}$, which are used to explain the non-specific interaction upon solvation of mixture of solvents on the incipient reactants and on the ion-pair. In addition, they are also subjected to multiparametric analysis employing Swain's solvent vectors A and B also with Kamlet–Taft's solvatochromic parameters α, β and π*. The reduction rates show an excellent correlation with multiparametric equations and are susceptible to both specific and non-specific solvation effects. A quantitative estimation of the latter components has been attempted.
Starting Page	212
Ending Page	218
Page Count	7
File Format	PDF
ISSN	03404285
Journal	Transition Metal Chemistry
Volume Number	26
Issue Number	1-2
e-ISSN	1572901X
Language	English
Publisher	Kluwer Academic Publishers
Publisher Date	2001-01-01
Publisher Place	Dordrecht
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Inorganic Chemistry Physical Chemistry
Content Type	Text
Resource Type	Article
Subject	Materials Chemistry Metals and Alloys Inorganic Chemistry

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