The interaction of an electrophilic carbene carbon atom with the π‐electron density of an aryl group favors an intramolecular migratory insertion reaction (see scheme; Pf=C6F5). This reaction gives alkyl compounds (2 or 3) which can be identified prior to their eventual hydrolysis to 4.

Transmetalation of an aminocarbene moiety from [W(CO)5{C(NEt2)R}] to palladium leads to isolable monoaminocarbene palladium aryl complexes [{Pd(mu-Br)Pf[C(NEt2)R]}2] (R = Me, Ph; Pf = C6F5). When [W(CO)5{C(OMe)R}] is used, the corresponding palladium carbenes cannot be isolated since these putative, more electrophilic carbenes undergo a fast migratory insertion process to give alkyl palladium complexes. These complexes could be stabilized in the eta3-allylic form for R = 2-phenylethenyl or in the less stable eta3-benzylic fashion for R = Ph. Hydrolysis products and a pentafluorophenylvinylic methyl ether (when R = Me) were also observed. The monoaminocarbenes slowly decompose through carbene-aryl coupling to produce the corresponding iminium salts and, depending on the reaction conditions, the corresponding hydrolysis products. The electrophilicity of the carbene carbon, which is mainly determined by the nature of the heteroatom group, controls the ease of evolution by carbene-aryl coupling. Accordingly, no carbene-aryl coupling was observed for a diaminocarbene palladium aryl complex.

Pentafluorophenyl palladium complexes 3 and 5 bearing a vinylcarbene ligand slowly decompose on heating by migratory insertion to give Pd(0) and the vinyliminium salts (Et 2 NdC(C 6 F 5 )CHdCHPh)X (X ) Br, BF 4 ). However, the presence of triphenylphosphine in complex 4 stabilizes 7, a compound with a CdC Pd-bound vinyliminium moiety, where there is a strong preference for the CdC versus the CdN coordination.

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