Ag(I)-Promoted Substitution of Cyanide from Hexacyanoferrate(II) with Pyrazine: A Kinetic and Mechanistic Study

Srivastava, Abhishek; Naik, Radhey Mohan; Rai, Jyotsana; Asthana, Abhas

doi:10.1134/s0036024421130227

Cited by 16 publications

(6 citation statements)

References 40 publications

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“…The fundamental importance and immediate applications of redox/ligand exchange reactions of transition metal complexes in synthetic, analytical, and organometallic chemistry attracted many chemists for their kinetic study [13][14][15][16][17][18]. Numerous kinetic reports on oxidation of Fe(II)/Co(II) complexes and the metalcatalyzed Hg(II)/Ag(I), cyanide substitution from cyano complexes of Fe(II)/Ru(II) by heterocyclic ligand containing nitrogen has been reported by several authors [19][20][21]. These reactions have also been successfully used for the micro-level quantification of employed catalysts and drugs/compounds that can bind strongly with a catalyst [22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Kinetic Study of Ru(III) Promoted Oxidation of L-Tryptophan in an Anionic Surfactant Medium by Hexacyanoferrate(III)

et al. 2023

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The kinetic investigation of Ru(III) promoted oxidation of L-tryptophan (Trp) by [Fe(CN)6]3- has been performed in anionic sodium dodecyl sulfate (SDS) micellar medium by recording the decrease in absorbance at 420 nm, corresponding to [Fe(CN)6]3- using UV-visible spectrophotometer. Pseudo-first-order condition has been used to examine the progress of reaction as a function of [Fe(CN)63−], ionic strength, [OH-], [SDS], [Ru3+], [Trp], and temperature by changing one variable at a time. The results exhibit that [OH-], [SDS], and [Trp] are the decisive parameter showing an appreciable effect on reaction rate. The reaction exhibits first-order kinetics in the studies concentration range of Ru(III), [Fe(CN)6]3− and at lower [Trp] and [OH-]. The incremental trend observed in the reaction rate with electrolyte concentration shows a positive salt effect. The reaction rate is almost ten times faster in SDS micellar medium compared to the aqueous medium. [Fe(CN)6]3- does not show any appreciable effect on the critical micellar concentration (CMC) of SDS as the polar head of SDS and [Fe(CN)6]3- both are negatively charged. The K+ obtained from K3[Fe(CN)6] and KNO3 decreases the repulsion between the negatively charged heads of the surfactant molecules thereby decreasing the CMC of SDS. The activation parameters also support the outer-sphere electron transfer mechanism as proposed by us. Resumen. El estudio cinético de la oxidación de L-tryptofano (Trp) con [Fe(CN)6]3- asistida por Ru(III), se llevó a cabo en un medio micelar de dodecilsulfato de sodio aniónico (SDS) y se monitoreó utilizando espectrometría de UV-visible midiendo la disminución de la absorbancia a 420 nm, correspondiente al [Fe(CN)6]3-. Para examinar el avance de la reaccción se utilizaron condiciones de pseudo-primer orden en función de [Fe(CN)63−], fuerza iónica, [OH-], [SDS], [Ru3+], [Trp], y temperatura, variando siempre una sola una variable. Los resultados indican, que los parametros decisivos que tuvieron un efecto apreciable sobre la velocidad de la reacción son [OH-], [SDS], y [Trp]. La reacción sigue una cinética de primer orden en el rango de concentraciones de estudio de Ru(III), [Fe(CN)6]3− y a bajas concentraciones de [Trp] y [OH-]. La tendencia de incremento de velocidad de la reacción con aumento de la concentración del electrolito muestra un efecto salino positivo. La velocidad de la reacción en el medio micelar de SDS es casi diez veces mayor que en solución acuosa. [Fe(CN)6]3- no muestra ningún efecto appreciable en la concentración crítica micelar (CMC) de SDS debido a que el grupo polar del SDS (SO3-, cabeza) y el [Fe(CN)6]3- tienen ambos carga negativa. Los cationes K+ provenientes del K3[Fe(CN)6] y KNO3 disminuyen la repulsión entre las cabezas con cargas negativas del surfactante, bajando así la CMC del SDS. Los parámetros de activación apoyan también el mecanismo de transferencia de electrones de la esfera exterior propuesto.

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Section: Introductionmentioning

confidence: 99%

Kinetic Study of Ru(III) Promoted Oxidation of L-Tryptophan in an Anionic Surfactant Medium by Hexacyanoferrate(III)

et al. 2023

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“…Numerous chemists were drawn to the kinetic study of the ligand substitution/redox reactions of transition metal complexes due to their fundamental significance and practical applications in synthetic, analytical, and organometallic chemistry 9–12 . Several authors have published kinetic reports on the substitution of cyanide from [Fe/Ru (CN) 6 ] 3− catalyzed by metal [Ag(I)/Hg(II)] and the oxidation of Co(II)/Fe(II) complexes 13–15 . Additionally, the trace‐level determination of used catalysts and medications/compounds that shows strong affinity towards catalyst has also been accomplished with success using these reactions 16–18 …”

Section: Introductionmentioning

confidence: 99%

Effect of cationic surfactant on Ru(III) catalyzed L‐glutamic acid oxidation by hexacyanoferrate(III)

Srivastava

Goswami

Dohare

et al. 2023

Int J of Chemical Kinetics

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In CTAB micellar medium, the kinetic investigation of Ru(III) promoted oxidation of L‐glutamic acid (Glu) by [Fe(CN)6]3− was carried out by recording the decline in absorbance at 420 nm, which corresponds to [Fe(CN)6]3−. By adjusting one variable at a time, the progression of the reaction has been inspected as a function of [OH−], ionic strength, [CTAB], [Ru3+], [Glu], [Fe(CN)63−], and temperature using the pseudo‐first‐order condition. The findings demonstrate that [OH−], [CTAB], and [Glu] are the key parameters that have a discernible impact on reaction rate. In the studied concentration range of Ru(III), [Fe(CN)6]3−, and at lower [Glu] and [OH−], the reaction displays first‐order kinetics. The incremental trend in reaction rate with electrolyte concentration demonstrates a positive salt effect. CTAB substantially catalyzes the process, and after reaching a maximum, the rate remains nearly constant at increased [CTAB]. The observed decline in the CMC of CTAB may be caused by the reduced repulsion between the positively charged heads of the surfactant molecules caused by the negatively charged OH−, and [Fe(CN)6]3−. The activation parameters also support the outer‐sphere electron transfer mechanism as recommended by us.

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“…In acidic medium, [Fe(CN) 6 ] 4À exists in its various protonated forms (Figure 1), The deprotonated form of [Fe(CN) 6 ] 4À is the most abundant ion at higher pH, while the tetraprotonated and diprotonated forms are predominant below pH 3.0 and within the 3.5-4.5 pH range, respectively (Perrin & Sayee, 1967;Srivastava et al, 2021).…”

Section: Introductionmentioning

confidence: 99%

“…The ultimate reaction product is formed by the reaction of 2,2′‐bipyridine (Bipy) with reactive aqua complex (Equation ()). The catalytic moiety (Hg 2+ ) regenerates itself in the presence of hydrogen ions via Equation ().

{[Fe {((), CN)}_{6}]}^{4 -} goodbreak+ {Hg}^{2 +} \overset{H_{2} normalO}{\to} {[Fe {((), CN)}_{5} \cdot {normalH}_{2} O]}^{3 -} goodbreak+ {HgCN}^{+}

{[Fe {((), CN)}_{5} \cdot {normalH}_{2} O]}^{3 -} goodbreak+ Bipy \to {[Fe {((), CN)}_{4} Bipy]}^{2 -} goodbreak+ H_{2} normalO

{HgCN}^{+} goodbreak+ H^{+} \to {Hg}^{2 +} goodbreak+ HCN

In acidic medium, [Fe(CN) 6 ] 4− exists in its various protonated forms (Figure 1), The deprotonated form of [Fe(CN) 6 ] 4− is the most abundant ion at higher pH, while the tetraprotonated and diprotonated forms are predominant below pH 3.0 and within the 3.5–4.5 pH range, respectively (Perrin & Sayee, 1967; Srivastava et al, 2021).…”

Section: Introductionmentioning

confidence: 99%

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Kinetic study of Hg(II)‐promoted substitution of cyanide from hexacyanoferrate(II) in an anionic surfactant medium by 2,2′‐bipyridine

Srivastava

Naik

Rai

et al. 2022

J Surfact & Detergents

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The kinetic investigation of Hg(II)‐promoted reaction between [Fe(CN)6]4− and 2,2′‐bipyridine (Bipy) has been performed in anionic sodium dodecyl sulfate (SDS) micellar medium by recording the surge in absorbance at 400 nm, corresponding to ultimate reaction product [Fe(CN)4 Bipy]2− using UV–visible spectrophotometer. Pseudo‐first‐order condition has been used to examine the progress of reaction as a function of temperature, [Fe(CN)64−], ionic strength, [SDS], pH, [Hg2+], and [Bipy] by changing one parameter at a time. The results exhibit that [Hg2+], [SDS], and pH are the decisive parameter showing maximum reaction rate at 1.5 × 10−4 mol dm−3, 6.0 × 10−3 mol dm−3, and 3.8, respectively. [Fe(CN)6]4− does not show any appreciable effect on the critical micellar concentration (CMC) of SDS as the polar head of SDS and [Fe(CN)6]4− both are negatively charged. Variable order kinetics was observed for [Fe(CN)6]4− and Bipy in their examined concentration range. The reverse response observed in the reaction rate with [KNO3] shows a negative salt effect. The K+ provided by K4[Fe(CN)6] and KNO3 decreases the repulsion between the negatively charged heads of the surfactant molecules thereby decreasing the CMC of SDS. The negative value for the entropy of activation also supports the interchange dissociative (Id) mechanism recommended by us.

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Ag(I)-Promoted Substitution of Cyanide from Hexacyanoferrate(II) with Pyrazine: A Kinetic and Mechanistic Study

Cited by 16 publications

References 40 publications

Kinetic Study of Ru(III) Promoted Oxidation of L-Tryptophan in an Anionic Surfactant Medium by Hexacyanoferrate(III)

Kinetic Study of Ru(III) Promoted Oxidation of L-Tryptophan in an Anionic Surfactant Medium by Hexacyanoferrate(III)

Effect of cationic surfactant on Ru(III) catalyzed L‐glutamic acid oxidation by hexacyanoferrate(III)

Kinetic study of Hg(II)‐promoted substitution of cyanide from hexacyanoferrate(II) in an anionic surfactant medium by 2,2′‐bipyridine

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