A Versatile Palladium Synthon: [Pd(NHC)(PhC≡CPh)]

The synthesis and isolation of [Pd(NHC)(PhC≡CPh)] complexes are reported. These new 14‐electron Pd(0)‐complexes are key synthons leading to known palladium(0) and palladium(II) species, as well as permitting access to unprecedented mixed NHC‐phosphite palladium(0) complexes. This motif permits the facile catalytic hydrosilylation of allenes. DFT calculations have allowed the characterization of the relatively weak interaction between the metal and the diphenylacetylene ligand, with a comparison with a series of ligands with more or less coordinating power, bearing varied structural and electronic properties. Low coordination number yet stable: The synthesis and characterisation of new low‐valent palladium (0) complexes are reported, and provide simple access to known and novel complexes, the instrinsic reactivity of which prevented their isolation using existing methods. One complex performs exceptionally well as a catalyst in the hydrosilylation reaction.