ABSTRACT
A series of palladium(ii) radical carbene complexes, [PCË(sp2)P]PdI, [PCË(sp2)P]PdBr, and [PCË(sp2)P]PdCl (PC(sp3)H2P = bis[2-(di-iso-propylphosphino)-phenyl]methane), is described. Compound [PCË(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 [PCË(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 n Bu3SnH.
