Related Experiment Video
Updated: May 1, 2026

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Mechanism of chromyl chloride alkane oxidation
Anthony K Rappe1, Maria Jaworska
1Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA. anthony.rappe@colostate.edu
Abstract:
Modern electronic structure methods, including complete active space-perturbation theory to second order (CASPT2) and a range of density functional (DFT) methods, are used to characterize the intermediates and transition states associated with chromyl chloride alkane oxidation. Computed energetics for radical abstraction are found to be inconsistent with experimental activation energetics. The alcohol product is also found to be too endothermic to be viable. A novel zwitterionic direct pathway is characterized which, when coupled with a dinuclear complex, exothermically produces alcohol consistent with experiment.
More Related Videos
10:10Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
Published on: July 28, 2018
09:54Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
Published on: September 12, 2018
Related Concept Videos
Halogenation of Alkenes
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Hydroboration-Oxidation of Alkenes
Electrophilic Addition to Alkynes: Hydrohalogenation
Radical Substitution: Halogenation of Alkanes and Alkyl Substituents
In the initiation step of the reaction, the chlorine molecule undergoes homolytic cleavage in the presence of light or heat, forming two highly reactive chlorine radicals. Propagation occurs in two...
Radical Substitution: Allylic Chlorination
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...