PdII complexes of donor-functionalized heterocyclic carbene ligands have been synthesized through a route involving carbene transfer from AgI carbene precursors. The Ag complexes undergo facile reaction with PdCl2(MeCN)2 to yield Pd(C∧OPh)2Cl2 (3a), Pd(C∧OOMe)2Cl2 (3b), and Pd(C∧N)2Cl2 (3c) (C∧OPh = 3-methyl-1-phenacylimidazolin-2-ylidene, C∧OOMe = 3-methyl-1-(methylacetyl)imidazolin-2-ylidene, C∧N = 3-methyl-1-picolylimidazolin-2-ylidene), from which [Pd(C∧OOMe)2(MeCN)2][BF4]2 (4b) and [Pd(C∧N)2][BF4]2 (4c) can be prepared by halide abstraction. When PdMeCl(cod) (cod = cyclooctadiene) is treated with the Ag complexes 2b and 2c, the Me−Pd carbene complexes [PdMe(C∧OOMe)Cl]2 (5b), PdMe(C∧N)Cl (5c), PdMe(C∧OOMe)2Cl (6b), and PdMe(C∧N)2Cl (6c) are obtained. The C∧OPh and C∧OOMe ligands are monodentate with a dangling functional moiety in all complexes, while the C∧N ligand exhibits both monodentate and chelating behavior. Several complexes give rise to highly active and very stable catalysts for Heck, Suzuki...