Related Experiment Video
Updated: Jul 31, 2025
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Unimolecular Reactivity of [Cu(R)(CF3 )3 ]- Complexes (R=Organyl): Stepwise versus Concerted Mechanism in
Bastian Zimmer1, Thomas Auth1, Konrad Koszinowski1,2
1Institut für Organische und Biomolekulare Chemie, Universität Göttingen, Tammannstr. 2, 37077, Göttingen, Germany.
Abstract:
The cuprate complexes [Cu(R)(CF3 )3 ]- (R=organyl) offer an efficient synthetic access to valuable trifluoromethylation products RCF3 . Here, electrospray-ionization mass spectrometry is used to analyze the formation of these intermediates in solution and probe their fragmentation pathways in the gas phase. Furthermore, the potential energy surfaces of these systems are explored by quantum chemical calculations. Upon collisional activation, the [Cu(R)(CF3 )3 ]- complexes (R=Me, Et, Bu, s Bu, allyl) afford the product ions [Cu(CF3 )3 ]⋅- and [Cu(CF3 )2 ]- . The former obviously results from an R⋅ loss, whereas the latter originates either from the stepwise release of R⋅ and CF3 ⋅ radicals or a concerted reductive elimination of RCF3 . The gas-phase fragmentation experiments as well as the quantum chemical calculations indicate that the preference for the stepwise reaction toward [Cu(CF3 )2 ]- increases with the stability of the formed organyl radical R⋅. This finding suggests that the recombination of R⋅ and CF3 ⋅ radicals may possibly contribute to the formation of RCF3 from [Cu(R)(CF3 )3 ]- in synthetic applications. In contrast, the [Cu(R)(CF3 )3 ]- complexes (R=aryl) only yield [Cu(CF3 )2 ]- when subjected to collision-induced dissociation. These species exclusively undergo a concerted reductive elimination because the competing stepwise pathway is disfavored by the low stability of aryl radicals.
More Related Videos
08:43Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives
Published on: January 19, 2016
10:10Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
Published on: July 28, 2018
Related Concept Videos
Acid Halides to Ketones: Gilman Reagent
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen...
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Preparation and Reactions of Sulfides
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...
Limitations of Friedel–Crafts Reactions