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Related Concept Videos

Introduction to Enzyme Kinetics01:19

Introduction to Enzyme Kinetics

Enzyme kinetics studies the rates of biochemical reactions. Scientists monitor the reaction rates for a particular enzymatic reaction at various substrate concentrations. Additional trials with inhibitors or other molecules that affect the reaction rate may also be performed.
The experimenter can then plot the initial reaction rate or velocity (Vo) of a given trial against the substrate concentration ([S]) to obtain a graph of the reaction properties. For many enzymatic reactions involving a...
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Kinetics describes the rate and path by which a reaction occurs. In contrast, thermodynamics deals with state functions and describes the properties, behavior, and components of a system. It is not concerned with the path taken by the process and cannot address the rate at which a reaction occurs. Although it does provide information about what can happen during a reaction process, it does not describe the detailed steps of what appears on an atomic or a molecular level. On the other hand,...
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Hot Biological Catalysis: Isothermal Titration Calorimetry to Characterize Enzymatic Reactions
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Published on: April 4, 2014

beta-Hydrogen Kinetic Effect.

Raffaello Romeo1, Giuseppina D'Amico, Emilia Sicilia

  • 1Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, Salita Sperone, 31-Vill. S. Agata-98166 Messina, Italy. rromeo@unime.it

Journal of the American Chemical Society
|April 6, 2007
PubMed
Summary

This study reveals that beta-hydrogens accelerate platinum complex isomerization via agostic interactions. These interactions stabilize intermediates, crucial for understanding alkane activation in catalysis.

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Area of Science:

  • Organometallic Chemistry
  • Computational Chemistry
  • Reaction Kinetics

Background:

  • Cationic platinum complexes undergo isomerization from cis to trans isomers.
  • The reaction mechanism involves solvent dissociation and intermediate formation.
  • The role of substituents and solvent interactions is not fully understood.

Purpose of the Study:

  • To investigate the uncatalyzed isomerization of cis-[Pt(R')(S)(PR3)2]+ to trans isomers.
  • To elucidate the mechanism, including rate-determining steps and intermediates.
  • To understand the influence of beta-hydrogens and agostic interactions on reaction rates.

Main Methods:

  • Combined kinetic experiments and Density Functional Theory (DFT) calculations.
  • Analysis of reaction pathways, transition states, and intermediate structures.
  • Quantification of dissociation energies and activation barriers.

Main Results:

  • The isomerization proceeds via solvent loss and T-shaped intermediates.
  • Beta-hydrogens significantly accelerate the reaction rate through the beta-hydrogen kinetic effect.
  • DFT confirms a Pt....eta2-HC agostic interaction in intermediates, stabilizing them by 21-33 kJ mol-1.

Conclusions:

  • Agostic interactions play a key role in stabilizing platinum complex intermediates.
  • Understanding these interactions is vital for controlling reaction pathways, particularly in alkane activation.
  • The beta-hydrogen kinetic effect provides a mechanism for accelerating these reactions.