Related Experiment Video
Updated: Jun 10, 2026

Thermochemical Studies of Ni(II) and Zn(II) Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
Kinetics of thermoneutral intermolecular hydrogen migration in alkyl radicals
Artur Ratkiewicz1, Barbara Bankiewicz, Thanh N Truong
1Chemistry Institute, University of Bialystok, Hurtowa 1, 15-399 Bialystok, Poland.
Abstract:
High pressure limits of thermal rate constants of intramolecular hydrogen migrations, particularly 1,3 to 1,6 H-shift in propyl, butyl, pentyl and hexyl radicals, respectively, were calculated using the canonical variational transition state theory (CVT) with a multi-dimensional small-curvature tunneling (SCT) correction over the temperature range of 300-3000 K. The CCSD(T)/cc-pVDZ//BH&HLYP/cc-pVDZ method was used to provide necessary potential energy surface information. Rate constants for these reactions were used to extrapolate rate constants for reactions of larger alkyls where experimental data are available using the Reaction Class Transition State Theory (RC-TST). Excellent agreement with experimental data confirms the validity of the RC-TST methodology and the accuracy of the calculated kinetic data in this study.
Related Concept Videos
Radical Anti-Markovnikov Addition to Alkenes: Thermodynamics
Radical Halogenation: Thermodynamics
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...
Reduction of Alkenes: Catalytic Hydrogenation
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Radical Chain-Growth Polymerization: Chain Branching

