Related Experiment Video
Updated: Jan 27, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Oxidation reactions of a nucleophilic palladium carbene: mono and bi-radical carbenes
Peng Cui1, Melissa R Hoffbauer, Mariya Vyushkova
1Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA. viluc@nd.edu.
Abstract:
Palladium(ii) cationic carbene radical and neutral bi-radical complexes were synthesized from a previously reported Pd(ii) carbene in the presence of one and two electron oxidants. When [{PC(sp2)P}tBuPd(PMe3)] (1, [PC(sp2)P]tBu = (bis[2-(di-iso-propylphosphino)-4-tertbutylphenyl]methylene)) was treated with [Cp2Fe][X] (X = BArF4, ArF = 3,5-(CF3)2C6H3, or PF6), the corresponding radical cationic complexes [{PC˙(sp2)P}tBuPd(PMe3)][X] (2: X = BArF4, 3: PF6) were isolated and characterized. Magnetic moment measurements and EPR spectroscopy indicated the presence of a ligand centered unpaired electron. In the presence of two electron oxidants such as 1,8-naphthylene disulfide or 9,10-anthracenedione, 1 converts to [{PC˙(sp2)P}tBuPdS(C10H6)SPd{PC˙(sp2)P}tBu] (4) or [{PC˙(sp2)P}tBuPdO(C14H10)OPd{PC˙(sp2)P}tBu] (5), respectively. Single crystal X-ray diffraction and EPR spectroscopy confirmed the bi-radical nature of 4 and 5.
More Related Videos
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
12:19Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Related Concept Videos
Radical Reactivity: Nucleophilic Radicals
Oxidation-Reduction Reactions
Nucleophilic Substitution Reactions
In 1896, the German chemist Paul Walden discovered that he could interconvert pure enantiomeric (+) and (-) malic acids through a series of reactions. This conversion suggested the involvement of optical inversion during the substitution reaction. Further, in 1930, Sir Christopher Ingold described for the first time two different forms of nucleophilic substitution reactions, which are known as SN1 (nucleophilic substitution unimolecular) and SN2 (nucleophilic substitution...
Radical Oxidation of Allylic and Benzylic Alcohols
Reactions of α-Halocarbonyl Compounds: Nucleophilic Substitution
Free-Radical Chain Reaction and Polymerization of Alkenes