Indices of transition state symmetry in proton-transfer reactions. Kinetic isotope effects and Bronested's .beta. in base-catalyzed diazo-coupling reactions

Hanna, Samir B.; Jermini, C.; Loewenschuss, Hana; Zollinger, Heinrich

doi:10.1021/ja00830a009

Cited by 11 publications

(2 citation statements)

References 3 publications

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“…In the experimental example , C was the ligand whereas D was the metal‐containing species H 2 OCbl + /HOCbl. This scheme seems to be often encountered in the literature of the kinetics of diverse chemical reactions . The rate equations based on this scheme are given as follows:

\begin{matrix} true \\ right \begin{matrix} \frac{d [normalC]}{d t} = - k_{3} [normalC] - k_{4} [normalC] [normalD] \\ \frac{d [normalD]}{d t} = - k_{4} [normalC] [normalD] \end{matrix} \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

Reaction Schemes That Are Easily Confused with a Reversible First-Order Reaction

Balogh

Lente

Kalmár³

et al. 2015

Int. J. Chem. Kinet.

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A detailed kinetic analysis of two schemes, one involving coupled consecutive processes and another featuring parallel reactions and decay of ???, is presented here using Taylor series expansion. It is shown that both of these schemes are easily confused with the reversible second order reaction in a routine kinetic study. The kinetic traces predicted by both schemes are sufficiently close to pseudo-first order curves so that it is practically impossible to identify the deviations based on data with the usual experimental errors, which was also demonstrated by fitting simulated theoretical curves to exponential functions. The dependence of the pseudo-first order rate constants on the concentration of the excess reagent features the same trend as in the case of a reversible reaction: a straight line with an intercept is observed. This analysis emphasizes that the reversible nature of reactions should be demonstrated by direct equilibrium studies, kinetic observations alone might be misleading.

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\begin{matrix} true \\ right \begin{matrix} \frac{d [normalC]}{d t} = - k_{3} [normalC] - k_{4} [normalC] [normalD] \\ \frac{d [normalD]}{d t} = - k_{4} [normalC] [normalD] \end{matrix} \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

Reaction Schemes That Are Easily Confused with a Reversible First-Order Reaction

Balogh

Lente

Kalmár³

et al. 2015

Int. J. Chem. Kinet.

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show abstract

“…Finally, a related reaction scheme of the type A + B -C where A also additionally spontaneously decomposes has been reported for the coupling of diazonium salts with 2-naphthol-6,8-disulfonic acid. 5 In this case data was collected under pseudo-first order conditions with B in excess, simplifying treatment of the data.…”

Section: Resultsmentioning

confidence: 99%

The effects of ligand decomposition on the pseudo first-order profile of a ligand substitution reaction: a “silent killer” in the background

et al. 2012

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ChemInform Abstract: MECHANISMS OF DIAZO COUPLING REACTIONS PART 28, INDICES OF TRANSITION STATE SYMMETRY IN PROTON‐TRANSFER REACTIONS, KINETIC ISOTOPE EFFECTS AND BRONSTED′S BETA IN BASE‐CATYLYZED DIAZO‐COUPLING REACTIONS

Hanna¹,

Jermini²,

Loewenschuss³

et al. 1975

Chemischer Informationsdienst

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Indices of transition state symmetry in proton-transfer reactions. Kinetic isotope effects and Bronested's .beta. in base-catalyzed diazo-coupling reactions

Cited by 11 publications

References 3 publications

Reaction Schemes That Are Easily Confused with a Reversible First-Order Reaction

Reaction Schemes That Are Easily Confused with a Reversible First-Order Reaction

The effects of ligand decomposition on the pseudo first-order profile of a ligand substitution reaction: a “silent killer” in the background

ChemInform Abstract: MECHANISMS OF DIAZO COUPLING REACTIONS PART 28, INDICES OF TRANSITION STATE SYMMETRY IN PROTON‐TRANSFER REACTIONS, KINETIC ISOTOPE EFFECTS AND BRONSTED′S BETA IN BASE‐CATYLYZED DIAZO‐COUPLING REACTIONS

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