Unveiling the mechanism of triphos-Ru catalysed C-O bond disconnections in polymers.

Ruthenium complexes with facially coordinating tripodal phosphine ligands are privileged catalysts for a broad range of (de-)hydrogenation-based transformations. Among these, C-O bond hydrogenolysis holds potential for the depolymerisation of both the biopolymer lignin and epoxy resins applied in wind turbine blades, aircrafts and more. However, this methodology is poorly understood in mechanistic terms. Here, we present a detailed investigation on the triphos-Ru catalysed C-O bond scission on a molecular level. A combination of experimental, spectroscopical and theoretical studies elucidates the reactivity of the ruthenium trimethylenemethane precatalyst, revealing the key roles of ruthenium phenolates in both catalyst activation as well as the catalytic cycle itself. Furthermore, a Ru(0)/Ru(II) oxidative addition into the C-O bond is disclosed, with a triphos-Ru(0) dihydrogen complex as entry point. With the molecular nature of the operating triphos-Ru species and the thermodynamics and kinetics of the catalysis unravelled, improvements of established methods as well as design of related transformations may become possible.

Catalytic disconnection of C-O bonds in epoxy resins and composites.

Fibre-reinforced epoxy composites are well established in regard to load-bearing applications in the aerospace, automotive and wind power industries, owing to their light weight and high durability. These composites are based on thermoset resins embedding glass or carbon fibres1. In lieu of viable recycling strategies, end-of-use composite-based structures such as wind turbine blades are commonly landfilled1-4. Because of the negative environmental impact of plastic waste5,6, the need for circular economies of plastics has become more pressing7,8. However, recycling thermoset plastics is no trivial matter1-4. Here we report a transition-metal-catalysed protocol for recovery of the polymer building block bisphenol A and intact fibres from epoxy composites. A Ru-catalysed, dehydrogenation/bond, cleavage/reduction cascade disconnects the C(alkyl)-O bonds of the most common linkages of the polymer. We showcase the application of this methodology to relevant unmodified amine-cured epoxy resins as well as commercial composites, including the shell of a wind turbine blade. Our results demonstrate that chemical recycling approaches for thermoset epoxy resins and composites are achievable.

Real-space, real-time approach to quantum-electrodynamical time-dependent density functional theory.

The quantum-electrodynamical time-dependent density functional theory equations are solved by time propagating the wave function on a tensor product of a Fock-space and real-space grid. Applications for molecules in cavities show the accuracy of the approach. Examples include the coupling strength and light frequency dependence of the energies, wave functions, optical absorption spectra, and Rabi splitting magnitudes in cavities, as well as a description of high harmonic generation in cavities.

Deformed explicitly correlated Gaussians.

Deformed explicitly correlated Gaussian (DECG) basis functions are introduced, and their matrix elements are calculated. All matrix elements can be calculated analytically in a closed form, except the Coulomb one, which has to be approximated by a Gaussian expansion. The DECG basis functions can be used to solve problems with nonspherical potentials. One example of such potential is the dipole self-interaction term in the Pauli-Fierz Hamiltonian. Examples are presented showing the accuracy and necessity of deformed Gaussian basis functions to accurately solve light-matter coupled systems in cavity QED.

Catalytic Hydrogenation of Polyurethanes to Base Chemicals: From Model Systems to Commercial and End-of-Life Polyurethane Materials.

Polyurethane (PU) is a highly valued polymer prepared from diisocyanates and polyols, and it is used in everyday products, such as shoe soles, mattresses, and insulation materials, but also for the construction of sophisticated parts of medical devices, wind turbine blades, aircrafts, and spacecrafts, to name a few. As PU is most commonly used as a thermoset polymer composed of cross-linked structures, its recycling is complicated and inefficient, leading to increasing PU waste accumulating every year. Catalytic hydrogenation represents an atom-efficient means for the deconstruction of polyurethanes, but so far the identification of an efficient catalyst for the disassembly of real-life and end-of-life PU samples has not been demonstrated. In this work, we reveal that a commercially available catalyst, Ir- iPrMACHO, under 30 bar H2 and 150-180 °C, is a general catalyst for the effective hydrogenation of the four cornerstones of PU: flexible solid, flexible foamed, rigid solid, and rigid foamed, leading to the isolation of aromatic amines and a polyol fraction. For the first time, a variety of commercial PU materials, including examples of foams, inline skating wheels, shoe soles, and insulation materials, has been deconstructed into the two fractions. Most desirable, our reaction conditions include the use of isopropyl alcohol as a representative of a green solvent. It is speculated that a partial glycolysis at the surface of the PU particles is taking place in this solvent and reaction temperatures in the presence of catalytic amounts of base. As such a more efficient hydrogenation of the solubilized PU fragments in isopropyl alcohol becomes possible. As the isolated anilines are precursors to the original isocyanate building blocks, and methods for their conversion are well-known, the work reported in this paper provides a realistic indication of a potential circular plastic economy solution for PU. Preliminary experiments were also undertaken applying Mn- iPrMACHO for the deconstruction of a commercial flexible PU foam. Although successful, more forcing conditions were required than those when applying Ir- iPrMACHO.

Experimental and theoretical studies on gold(III) carbonyl complexes: reductive C,H- and C,C bond formation.

The reactivity of cationic (C^C)gold(iii) carbonyl complexes was investigated. While the in situ-formed IPrAu(bph)CO+ complex (bph = biphenyl-2,2'-diyl) does not undergo a migratory insertion of CO into the neighboring gold-carbon bond, nucleophiles can attack the coordinated CO moiety intermolecularly. Water as a nucleophile initiates a CO2 extrusion combined with a reductive C,H bond formation. The rapid formation of a gold(i) species from an intermediary gold(iii) carbonyl has not been observed before and shows a significant difference in reactivity between (C^C) and (C^N^C)gold(iii) carbonyls. The latter have been reported to form stable gold(iii) hydrides via the WGS reaction. In the case of methanol acting as a nucleophile attacking the gold(iii) carbonyl, no extrusion of CO2 is observed. Instead an intermediary gold(iii) carboxyl complex forms an aryl carboxylate via reductive C-C bond elimination. Experimental and theoretical studies on the mechanism explain the observed selectivities and give new insights into the reactivity of elusive gold(iii) carbonyls.

The Influence of Implant Site Preparation and Sterilization on the Performance and Wear of Implant Drills.

PURPOSE: The aim of this study was to investigate if repeated use of pilot and depth drills for implant site preparation in combination with resterilization leads to any significant changes in cutting edges or in preparation times. MATERIALS AND METHODS: With drills of different lengths and widths (pilot, parallel, and tapered), osteotomies were performed under constant conditions in pig jaws. After each osteotomy, the drills were processed and sterilized. The required time for finishing the osteotomy was noted and analyzed. At the end of each osteotomy cycle, consisting of 10 osteotomies and 10 sterilizations, the cutting edge wear of the drill was analyzed using scanning electron microscopy. Unused but sterilized drills served as a control group. RESULTS: There was no statistically significant difference in the evaluated wear between pilot drills and depth drills as well as between the test and the control group. After 60 osteotomies, implant drills showed considerable signs of wear at the major cutting edge (P > .05). Osteotomy led to a significant increase in the drilling time. While pilot drills showed an increase of drilling time of the factor 33.3, and the tapered drills of the factor 5.37, the parallel drills remained constant in their performance. CONCLUSION: Within the limitations of this study, it can be concluded that the process of sterilization as well as the number of performed osteotomies play a major role in the wear of the cutting edge and the performance of implant drills.

Stochastic Variational Approach to Small Atoms and Molecules Coupled to Quantum Field Modes in Cavity QED.

In this work, we present a stochastic variational calculation (SVM) of energies and wave functions of few particle systems coupled to quantum fields in cavity QED. The spatial wave function and the photon spaces are optimized by a random selection process. Using correlated basis functions, the SVM approach solves the problem accurately and opens the way to the same precision that is reached the nonlight coupled quantum systems. Examples for a two-dimensional trion and confined electrons as well as for the He atom and the H_{2} molecule are presented showing that the light-matter coupling drastically changes the electronic states.

Synthesis of Fulvene Vinyl Ethers by Gold Catalysis.

Gold-catalyzed cyclization of 1,5-diynes with ketones as reagents and solvent provides diversely substituted vinyl ethers under mild conditions. The regioselectivity of such gold-catalyzed cyclizations is usually controlled by the scaffold of the diyne. Herein, we report the first solvent-controlled switching of regioselectivity from a 6-endo-dig- to 5-endo-dig-cyclization in these transformations, providing fulvene derivatives. With respect to the functional-group tolerance, aryl fluorides, chlorides, bromides, and ethers are tolerated. Furthermore, the mechanism and selectivity are put to scrutiny by experimental studies and a thermodynamic analysis of the product. Additionally, 6-(vinyloxy)fulvenes are a hitherto unknown class of compounds. Their reactivity is briefly evaluated, to give insights into their potential applications.

Insights into the gold-catalyzed propargyl ester rearrangement/tandem cyclization sequence: radical versus gold catalysis-Myers-Saito- versus Schmittel-type cyclization.

A detailed study of the gold-catalyzed tandem 1,3-carboxy migration/allene-enyne cycloisomerization was undertaken. It was found that after the initial allene formation the selectivity of the reaction is strongly influenced by the polarization of the remaining alkyne. Depending on the substitution pattern of the starting diynes, either a Schmittel- or a Myers-Saito-type cyclization was triggered. The 6-endo-dig Myers-Saito-type cyclization gave access to benzo[b]fluorenes, while the Schmittel pathway (5-exo-dig) delivered benzofulvenes as final products. In special cases a yet unknown pathway was opened by the ambiphilic nature of the allene moiety. In these cases completely different products were obtained by the nucleophilic attack of the alkyne moiety onto the allene that can also act as an electrophile. Mechanistic studies revealed that diradical pathways can be ruled out for this type of tandem cyclization reactions and it is shown that both steps of the reaction cascade are catalyzed by the gold complex.

Synthesis of highly substituted γ-butyrolactones by a gold-catalyzed cascade reaction of benzyl esters.

Easily accessible benzylic esters of 3-butynoic acids in a gold-catalyzed cyclization/rearrangement cascade reaction provided 3-propargyl γ-butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C-C bond is an intermolecular process. Initially propargylic-benzylic esters were used, but alkyl-substituted benzylic esters worked equally well. In the case of the propargylic-benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl-substituted γ-butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one-pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact.