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Issue 8, 2015
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Palladium carbene complexes as persistent radicals

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Abstract

A series of palladium(II) radical carbene complexes, [PC˙(sp2)P]PdI, [PC˙(sp2)P]PdBr, and [PC˙(sp2)P]PdCl (PC(sp3)H2P = bis[2-(di-iso-propylphosphino)-phenyl]methane), is described. Compound [PC˙(sp2)P]PdI dimerizes to {[PC(sp2)P]PdI}2 in the solid state, akin to the formation of Gomberg's dimer. While the bromo and the iodo derivatives could be obtained from the oxidation of [PC(sp2)P]Pd(PMe3) by the respective dihalogens, a halogen transfer reaction from CH2Cl2 was used for the formation of [PC˙(sp2)P]PdCl. The halogen transfer from CH2X2 (X = Cl, Br, I) could be used to obtain all three radical carbene palladium complexes and also allowed the isolation of [PC(CH2)P]Pd(PMe3), which is the result of methylene group transfer from CH2X2. Compound [PC(CH2)P]Pd(PMe3) was independently synthesized from [PC(CH3)HP]PdCl2, which contains a supporting ligand analogous to that of the radical carbene complexes but has one of the hydrogen atoms replaced by a methyl group. All three carbene radical species abstract a hydrogen from 9,10-dihydroanthracene or nBu3SnH.

Graphical abstract: Palladium carbene complexes as persistent radicals

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Publication details

The article was received on 21 Apr 2015, accepted on 18 May 2015 and first published on 18 May 2015


Article type: Edge Article
DOI: 10.1039/C5SC01441G
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Citation: Chem. Sci., 2015,6, 4570-4579
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    Palladium carbene complexes as persistent radicals

    C. C. Comanescu, M. Vyushkova and V. M. Iluc, Chem. Sci., 2015, 6, 4570
    DOI: 10.1039/C5SC01441G

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