N-Heterocyclic carbene gold(I) complexes [(L)AuCl] [L = 1,3-diethyl-4,5-dihydroimidazol-2-ylidene (3a); 1,3-dibenzyl-4,5-dihydroimidazol-2-ylidene (3c); 1,3-dipicolyl-4,5-dihydroimidazol-2-ylidene (3d); 1,3-diethylimidazol-2-ylidene (5a); and 1-methylthiomethyl-3-mesitylimidazol-2-ylidene (10)] react with [(PhCN)2PdCl2] to give the corresponding palladium complexes, and the reactions are promoted by the addition of triphenylphosphine. This study demonstrates that the carbene moiety can be transferred from Au(I) to Pd(II) for the first time.

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Formation of the N-arylated η 3 -aza-TMM complexes of iridium from regioselective hydroanilination of an octahedral (η 1 -allenyl)iridium complex has been studied. (OC-6-42)-In contrast, the reactions of 2 with XC 6 H 4 NH 2 (X ) F, NO 2 , MeO, H, Me), Ph 2 NH, and Ph(Me)NH result in regioselective addition at the allenyl ligand, thereby generating the N-arylated η 3 -aza-TMM complexes 5a-g. The mechanistic studies confirm that the hydroanilination is preceded by the formation of an aniline-ligated intermediate. † Based on the M.S. thesis of Y.-K.C.,

A number of palladium(ii) complexes with a heteroditopic NHC-amine ligand and their precursor silver(i) carbene complexes have been efficiently prepared and their structural features have been investigated. The heteroditopic coordination of this ligand class was unequivocally shown by NMR-spectroscopy and X-ray crystallographic analysis. The neutral and cationic cis-methyl-palladium(NHC) complexes are not prone to reductive elimination, which is normally a major degenerative pathway for this type of complex. In contrast, under carbon monoxide atmosphere rapid reductive elimination of the acyl-imidazolium salt was observed.