Issue 26, 2019

Oxidation reactions of a nucleophilic palladium carbene: mono and bi-radical carbenes

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.

Graphical abstract: Oxidation reactions of a nucleophilic palladium carbene: mono and bi-radical carbenes

Supplementary files

Article information

Article type
Paper
Submitted
07 Feb 2019
Accepted
12 Mar 2019
First published
12 Mar 2019

Dalton Trans., 2019,48, 9663-9668

Author version available

Oxidation reactions of a nucleophilic palladium carbene: mono and bi-radical carbenes

P. Cui, M. R. Hoffbauer, M. Vyushkova and V. M. Iluc, Dalton Trans., 2019, 48, 9663 DOI: 10.1039/C9DT00585D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements