NDLI: Kinetics of cetyl trimethyl ammonium bromide catalyzed substitution of tris(sulfonated triazine)iron(II) complexes by 1,10-phenanthroline, 2,2′-bipyridine and 2,2′,6,2″-terpyridine

Content Provider	Springer Nature Link
Author	Bellam, Rajesh Anipindi, Nageswara Rao
Copyright Year	2014
Abstract	The kinetics of substitution of tris(3-(2-pyridyl)-5,6-bis(4-phenyl-sulfonic acid)-1,2,4-triazine)-iron(II), $$ {\text{Fe}}({\text{PDTS}})_{3}^{4 - } $$ , and tris(3-(4-(4-phenylsulfonic acid)-2-pyridyl)-5,6-bis(4-phenylsulfonic acid)-1,2,4-triazine)-iron(II), $$ {\text{Fe}}({\text{PPDTS}})_{3}^{7 - } $$ , by two polypyridyls, namely 2,2′-bipyridine (bpy) and 2,2′,6′,2″-terpyridine (terpy), have been studied at 25–55 °C under pseudo-first-order conditions, i.e., [ppy] ≫ $$ [{\text{Fe}}({\text{PDTS}})_{3}^{4 - } ] $$ or $$ [{\text{Fe}}({\text{PPDTS}})_{3}^{7 - } ] $$ in acetate buffers over the pH range 3.6–5.6 (ppy = bpy, terpy or phen). The reactions are first order in $$ {\text{Fe}}({\text{PDTS}})_{3}^{4 - } $$ or $$ {\text{Fe}}({\text{PPDTS}})_{3}^{7 - } $$ . The reaction rates increase with [ppy] and pH. Plots of k $_{obs}$ versus [ppy] and 1/[H$^{+}$] are linear with positive intercepts on the rate axes, indicating that the reactions proceed by both ppy- and hydrogen ion-dependent and independent paths. Ionic strength has no influence on the rate of reaction. Cetyl trimethyl ammonium bromide (CTAB) catalyzes these substitution processes, including substitution by 1,10–phenanthroline (phen). The micelle-catalyzed reactions essentially follow the same general pattern as the uncatalyzed reactions. Micellar catalysis is ascribed to the binding of the anionic substrate on the surface of the cationic surfactant by hydrophilic and/or electrostatic interactions and significant electrostatic contribution to the binding of the positively charged quaternary ammonium head group to π-electron-rich polypyridyls. Kinetic data have been obtained at three different temperatures, and the specific rate constants (k $_{1}$ and k $_{2}$) and thermodynamic parameters (E $_{a}$, ΔS $^{#}$ and ΔG $^{#}$) have been computed. The binding constants between $$ {\text{Fe}}({\text{PDTS}})_{3}^{4 - } $$ / $$ {\text{Fe}}({\text{PPDTS}})_{3}^{7 - } $$ and CTAB have been evaluated. The near-equal values of ΔG $^{#}$ obtained in aqueous and CTAB media suggest that these reactions occur by essentially the same mechanism in either medium.
Starting Page	311
Ending Page	326
Page Count	16
File Format	PDF
ISSN	03404285
Journal	Transition Metal Chemistry
Volume Number	39
Issue Number	3
e-ISSN	1572901X
Language	English
Publisher	Springer International Publishing
Publisher Date	2014-02-13
Publisher Place	Cham
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Catalysis Physical Chemistry Inorganic Chemistry
Content Type	Text
Resource Type	Article
Subject	Materials Chemistry Metals and Alloys Inorganic Chemistry

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