A novel anionic N-heterocyclic carbene was prepared and ligated to [Pd(allyl)Cl] 2 to yield the complex (NHC-enolate)Pd(allyl). At elevated temperatures in acetonitrile, the allyl ligand undergoes a stereoselective η 3 -η 1 -η 3 isomerization in an associative process that is first order in CD 3 CN with ∆H q ) 13.5 ( 0.7 kcal mol -1 and ∆S q ) -17 ( 2 eu. This complex reacts with electrophiles (HCl, CH 3 I) at the enolate position.

Two novel N-heterocylic carbene enolate nickel complexes have been prepared and shown to be active for ethylene and propylene polymerization to yield linear polymers.

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