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The reduction of γ-Al2O3-supported PdO in flowing aqueous ethanol was investigated. Quick EXAFS (QEXAFS) performed at the Pd K-edge reveals that the presence of Cl can have a profound effect on the reduction process. At low loadings of Pd (1 wt-%), the size dependency of the process is inverted, compared to Cl-free samples. The extent of reduction was found to be dependent on loading/particles size. It is shown, using in situ QEXAFS at the Cl K- and Pd L3-edges, that residual Cl is not removed by the flowing solvent mixture, even at an elevated temperature of 350 K. The origins of these behaviours are discussed in terms of the differing effects that Cl may have when bonded to oxidic or reduced metal centres and the results were compared to earlier observations made on the effects of Cl on commercial polyurea encapsulated Pd ENCAT™ NP 30 catalysts.

International audience; Ethanol-water, a prototypical 'green' solvent mixture, cannot be considered as inert toward supported Pd nanoparticles. We establish severe size dependencies in Pd redox behavior, persistent gradients in Pd phase in a plug-flow situation, and that Pd nanoparticles are contaminated with hydrogen derived from the solvent

Transmission electron microscopy (TEM) is commonly used as an ex-situ technique to determine structural changes by comparing images of catalyst particles before and after a reaction. This requires the use of an alcoholic solvent to disperse the particles on a grid. In this work, we will show that Pd catalysts can be transformed during the procedure, by using EXAFS to determine the structure of Pd catalysts in different environments (as dry or wet samples). Supported palladium nanoparticles exposed to aqueous ethanolic solution (50% w/v) are transformed to a common, reduced, and hydrogen-contaminated state, irrespective of their initial habit or support. Catalysts comprised of nanosize PdO are reduced at ca. 350 K, whereas samples comprised of very small (ca. ≤ 10 atoms) Pd particles react with the solvent at just above room temperature and agglomerating with considerable loss of dispersion. As such any potential benefits to catalysis sought through the synthesis of very highly dispersed metallic Pd supported upon a range of inorganic dispersants will be rapidly erased through the action of such solvents.

In situ X-ray absorption spectroscopy (XAS) and Pd K, LIII, and Cl K-edges shows that Cl can be present in significant amounts in ENCAT™ 30 catalysts and that it can severely retard Pd nanoparticle (NP) development in flowing solvents. We also show that whilst polymeric encapsulation protects the Pd against solvent induced agglomeration of Pd nanoparticles the evidence suggests it does not prevent the formation PdHx through reaction with the aqeous ethanol solvent, and that, as received, ENCAT™ 30 NP catalysts are not, for the most part, comprised of nanoparticulate Pd0 irrespective of the presence of Cl.\ud \ud

The nuclearity and structures of the palladium complex [(SPhos)Pd(Ph)Cl]

The nuclearity and structures of the palladium complex [(SPhos)Pd(Ph)Cl]2 in the solid and solution states are revisited using a combination of Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, NMR spectroscopy, mass spectrometry, DFT calculations and trapping experiments. The complex was tested for its catalytic activity in the coupling reaction between chlorobenzene and n-hexylamine, where different deactivation behaviours were observed in toluene, 1,4-dioxane and DMF.

The role of chiral counterions in gold-catalyzed asymmetric intramolecular hydroamination/hydroalkoxylation reactions of allenes and the oxidation state of the gold catalyst in the benzannulation of 2-carbonylphenylalkynes have been investigated using XAFS at the L3 edge of gold. Fitting of experimental data indicated a bond between cationic gold and a BINOL-phosphate anion in solution. 31P NMR confirmed that this phosphate group is likely not to be labile and may stay bonded to the gold catalyst during the catalytic cycle. In the benzannulation reaction, XAFS analysis suggested the majority of gold species obtained from reacting starting material with AuCl3 to be Au(III) complexes. NMR and mass spectrometry characterization led to the previously unobserved intermediate 10. gem-Diaurate complexes, which have been previously proposed as possible intermediates, were not detected.

Experimental support for the dominance of van der Waals dispersion forces in aromatic stacking interactions occurring in organic solution is surprisingly limited. Here, we have examined the size-dependence of aromatic stacking in an organic solvent. The interaction energy was found to vary by ~7.5 kJ mol–1 on going from a phenyl-phenyl to an anthracene-pyrene stack. Strikingly, the experimental data were highly correlated with dispersion energies determined using symmetry-adapted perturbation theory (SAPT), while the induction, exchange, electrostatic and solvation energy components correlated poorly. Both the experimental data and the SAPT-dispersion energies gave high-quality correlations with the change in solvent accessible area upon complexation. Thus, the size-dependence of aromatic stacking interactions is consistent with the dominance of van der Waals dispersion forces even in the presence of a competing polarizable solvent.

The 2–4 keV energy range provides a rich window into many facets of materials science and chemistry. Within this window, P, S, Cl, K and CaK-edges may be found along with theL-edges of industrially important elements from Y through to Sn. Yet, compared with those that cater for energies aboveca.4–5 keV, there are relatively few resources available for X-ray spectroscopy below these energies. In addition,in situoroperandostudies become to varying degrees more challenging than at higher X-ray energies due to restrictions imposed by the lower energies of the X-rays upon the design and construction of appropriate sample environments. The XMaS beamline at the ESRF has recently made efforts to extend its operational energy range to include this softer end of the X-ray spectrum. In this report the resulting performance of this resource for X-ray spectroscopy is detailed with specific attention drawn to: understanding electrostatic and charge transfer effects at the SK-edge in ionic liquids; quantification of dilution limits at the ClK- and RhL3-edges and structural equilibria in solution; in vacuum deposition and reduction of [RhI(CO)2Cl]2to γ-Al2O3; contamination of γ-Al2O3by Cl and its potential role in determining the chemical character of supported Rh catalysts; and the development of chlorinated Pd catalysts in `green' solvent systems. Sample environments thus far developed are also presented, characterized and their overall performance evaluated.

A custom-made plug flow reactor was designed and constructed to examine the behaviour of Pd catalysts during Suzuki-Miyaura cross-coupling reactions. Spatial-temporal resolution of catalyst activation, deactivation and leaching processes can be obtained by single-pass experiments. Subsequent deployment of the flow reactor in a XAS beam line revealed speciation of Pd along the catalyst bed.

Formation of iminium ions from the condensation of chiral secondary or primary amines with alpha,beta-unsaturated aldehydes or ketones can be used as an effective platform for the acceleration of a wide variety of catalytic asymmetric cycloaddition and conjugate addition reactions. The reversible formation of the active iminium ion species simulates the pi-electronics and equilibrium dynamics traditionally associated with Lewis acid activation of alpha,beta-unsaturated carbonyl compounds lowering the energy level of the LUMO associated with the pi-system and activating subsequent reaction. Importantly, these iminium ion catalysed processes offer the opportunity to conduct reactions in the presence of both moisture and air greatly adding to the practicality and general applicability of the chemistry described. Proposed catalytic cycles and transition state models for the induction of asymmetry provide reliable and robust predictive tools for the outcome of reactions and high functional group tolerance suggests this class of transformation will have broad application in the arena of synthetic organic chemistry as the area matures. This review describes the rapid expansion of iminium ion catalysis over recent years from its conceptual introduction to the development of a whole new arsenal of highly practical and effective methods with which to approach challenging and fundamental bond construction processes.

Formation of iminium ions from the condensation of chiral secondary or primary amines with a,b-unsaturated aldehydes or ketones can be used as an effective platform for the acceleration of a wide variety of catalytic asymmetric cycloaddition and conjugate addition reactions. The reversible formation of the active iminium ion species simulates the π-electronics and equilibrium dynamics traditionally associated with Lewis acid activation of a,b-unsaturated carbonyl compounds lowering the energy level of the LUMO associated with the π-system and activating subsequent reaction. Importantly, these iminium ion catalysed processes offer the opportunity to conduct reactions in the presence of both moisture and air greatly adding to the practicality and general applicability of the chemistry described. Proposed catalytic cycles and transition state models for the induction of asymmetry provide reliable and robust predictive tools for the outcome of reactions and high functional group tolerance suggests this class of transformation will have broad application in the arena of synthetic organic chemistry as the area matures. This review describes the rapid expansion of iminium ion catalysis over recent years from its conceptual introduction to the development of a whole new arsenal of highly practical and effective methods with which to approach challenging and fundamental bond construction processes.

Formation of iminium ions from the condensation of chiral secondary or primary amines with a,b-unsaturated aldehydes or ketones can be used as an effective platform for the acceleration of a wide variety of catalytic asymmetric cycloaddition and conjugate addition reactions. The reversible formation of the active iminium ion species simulates the π-electronics and equilibrium dynamics traditionally associated with Lewis acid activation of a,b-unsaturated carbonyl compounds lowering the energy level of the LUMO associated with the π-system and activating subsequent reaction. Importantly, these iminium ion catalysed processes offer the opportunity to conduct reactions in the presence of both moisture and air greatly adding to the practicality and general applicability of the chemistry described. Proposed catalytic cycles and transition state models for the induction of asymmetry provide reliable and robust predictive tools for the outcome of reactions and high functional group tolerance suggests this class of transformation will have broad application in the arena of synthetic organic chemistry as the area matures. This review describes the rapid expansion of iminium ion catalysis over recent years from its conceptual introduction to the development of a whole new arsenal of highly practical and effective methods with which to approach challenging and fundamental bond construction processes.

A combination of solution phase NMR, X-ray crystallographic studies, and DFT calculations provide a consistent structural conformation for iminium ions derived from the MacMillan imidazolidinone.