Correlation of Experimental and Calculated Reaction Enthalpies with Ligand Donor Strengths.

Ylide-functionalized phosphines (YPhos) have recently proven to be strongly donating ligands that enable high catalyst activities in gold(I)-mediated transformations. We now report on a calorimetric study dealing with the [Au(YPhos)Cl] system and assess YPhos-Au bond dissociation enthalpies (BDE). Comparison with other commonly used phosphines confirmed the high binding strengths of the YPhos ligands. Furthermore, the values of the reaction enthalpies were shown to correlate with the electronic properties of the ligands measured via the Tolman electronic parameter or the calculated molecular electrostatic potential at phosphorus. Notably, the reaction enthalpies can conveniently be derived by computational methods, thus making these easy-to-obtain descriptors for ligand donor property quantification.

Synthesis of Gold(I)-Trifluoromethyl Complexes and their Role in Generating Spectroscopic Evidence for a Gold(I)-Difluorocarbene Species.

Readily prepared and bench-stable [Au(CF3 )(NHC)] compounds were synthesized by using new methods, starting from [Au(OH)(NHC)], [Au(Cl)(NHC)] or [Au(L)(NHC)]HF2 precursors (NHC=N-heterocyclic carbene). The mechanism of formation of these species was investigated. Consequently, a new and straightforward strategy for the mild and selective cleavage of a single carbon/fluorine bond from [Au(CF3 )(NHC)] complexes was attempted and found to be reversible in the presence of an additional nucleophilic fluoride source. This straightforward technique has led to the unprecedented spectroscopic observation of a gold(I)-NHC difluorocarbene species.

Au⋠⋠⋠H-C Hydrogen Bonds as Design Principle in Gold(I) Catalysis.

Secondary ligand-metal interactions are decisive in many catalytic transformations. While arene-gold interactions have repeatedly been reported as critical structural feature in many high-performance gold catalysts, we herein report that these interactions can also be replaced by Au⋅⋅⋅H-C hydrogen bonds without suffering any reduction in catalytic performance. Systematic experimental and computational studies on a series of ylide-substituted phosphines featuring either a PPh3 (Ph YPhos) or PCy3 (Cy YPhos) moiety showed that the arene-gold interaction in the aryl-substituted compounds is efficiently compensated by the formation of Au⋅⋅⋅H-C hydrogen bonds. The strongest interaction is found with the C-H moiety next to the onium center, which due to the polarization results in remarkably strong interactions with the shortest Au⋅⋅⋅H-C hydrogen bonds reported to date. Calorimetric studies on the formation of the gold complexes further confirmed that the Ph YPhos and Cy YPhos ligands form similarly stable complexes. Consequently, both ligands showed the same catalytic performance in the hydroamination, hydrophenoxylation and hydrocarboxylation of alkynes, thus demonstrating that Au⋅⋅⋅H-C hydrogen bonds are equally suited for the generation of highly effective gold catalysts than gold-arene interactions. The generality of this observation was confirmed by a comparative study between a biaryl phosphine ligand and its cyclohexyl-substituted derivative, which again showed identical catalytic performance. These observations clearly support Au⋅⋅⋅H-C hydrogen bonds as fundamental secondary interactions in gold catalysts, thus further increasing the number of design elements that can be used for future catalyst construction.

PMO-Immobilized AuI -NHC Complexes: Heterogeneous Catalysts for Sustainable Processes.

A stable periodic mesoporous organosilica (PMO) with accessible sulfonic acid functionalities is prepared via a one-pot-synthesis and is used as solid support for highly active catalysts, consisting of gold(I)-N-heterocyclic carbene (NHC) complexes. The gold complexes are successfully immobilized on the nanoporous hybrid material via a straightforward acid-base reaction with the corresponding [Au(OH)(NHC)] synthon. This catalyst design strategy results in a boomerang-type catalyst, allowing the active species to detach from the surface to perform the catalysis and then to recombine with the solid after all the starting material is consumed. This boomerang behavior is assessed in the hydration of alkynes. The tested catalysts were found to be active in the latter reaction, and after an acidic work-up, the IPr*-based gold catalyst can be recovered and then reused several times without any loss in efficiency.

Gold complexes with remote-substituted amino N-heterocyclic carbenes.

The 4-RN-1,3-Ar2-imidazolium salt, R = iPr, tBu, Ar = Mes, Dipp, Mes = mesityl, Dipp = 2,6-bis-diisopropyl-phenyl was metalated by AuI at the C2-, C5- and 4-RN positions depending on the reactants and conditions employed; a rare direct rearrangement of a AuI aminide to an abnormal imidazol-5-ylidene AuI complex was also observed and based on a DFT study it may involve TfO- facilitated H+ transfer.

Synthesis and catalytic activity of palladium complexes bearing N-heterocyclic carbenes (NHCs) and 1,4,7-triaza-9-phosphatricyclo[5.3.2.1]tridecane (CAP) ligands.

The synthesis and characterization of novel palladium complexes bearing N-heterocyclic carbenes (NHCs) and 1,4,7-triaza-9-phosphatricyclo[5.3.2.1]tridecane (CAP) are reported. These organometallic complexes can be easily obtained using two different synthetic strategies that involve either the substitution of the pyridine ligand from trans-[Pd(NHC)(Py)Cl2] or by simple addition of the CAP ligand to dimeric species [Pd(NHC)Cl2]2. The mixed NHC/CAP complexes were tested as pre-catalysts in the Buchwald-Hartwig aryl amination coupling, showing good catalytic activity, especially in the case of cis-[Pd(IPr)(CAP)Cl2].