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

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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

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Publication details

The article was received on 07 Feb 2019, accepted on 12 Mar 2019 and first published on 12 Mar 2019


Article type: Paper
DOI: 10.1039/C9DT00585D
Citation: Dalton Trans., 2019, Advance Article

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    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, Advance Article , DOI: 10.1039/C9DT00585D

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