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Despite the widespread use of well-defined PdII complexes as pre-catalysts for cross-coupling processes, the role of the throw-away ligand is still underexplored. In this work we focused on the complexes of the type [Pd(NHC)(η3-R-allyl)Cl] (NHC = N-heterocyclic carbene) and we investigated the influence of the R substitution on the allyl moiety. Starting from the already described [Pd(IPr)(η3-cinnamyl)Cl] and [Pd(IPr*)(η3-cinnamyl)Cl] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, IPr* = N,N′-1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]imidazol-2-ylidene) we prepared eight new complexes bearing new substitutions on the cinnamyl motif and we tested them in the C–N bond formation to evaluate the effect of the throw-away ligand modification in the catalytic activity. In addition, we studied the undesired formation of the less active off-cycle [Pd I2 (NHC)2(η3-R-allyl)(μ-Cl)] dimers from the corresponding PdII complexes to evaluate the role of the new throw-away ligands on the inhibition of this process. [ABSTRACT FROM AUTHOR]

The intricate σ and π-bonding of N-heterocyclic carbenes (NHCs) to metals and the need to quantify their electronic properties to rationalize reactivity of complexes have resulted in the creation of numerous methodologies to understand the NHC–metal interaction which are, as we now show, flawed. Our search for a unified, easily accessible system to gauge these fundamental properties has resulted in the discovery of two systems that highlight the flaws present in existing systems and provide a more accurate measure of the NHC ligand electronic properties. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]