Dimerization of a mixed-carbene Pd dibromide complex by elemental iodine.

A monomeric Pd complex bearing a mixed carbocyclic/N-heterocyclic carbene ligand and two bromides was reacted with an excess of elemental iodine, which resulted in the surprising removal of one bromide ligand and dimerization of the mixed-carbene complex to form di-μ-bromido-bis{[1-(cyclohepta-2,4,6-trien-2-yl-1-ylidene-κC)-3-(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II)} bis(pentaiodide) dichloromethane monosolvate, [PdBr(CHN)](I)·CHCl. The dimeric complex features a slightly distorted square-planar core of two Pd centres bridged by two bromide ligands, which lie in the same plane as the seven- and five-membered rings of the bidentate carbene ligand. The counter-ions in the single crystal were found to be pentaiodide monoanions featuring their typical V-shape, whereas for the bulk material, a mixture of Br/I interhalides is proposed.