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- ItemProbing Oxide Reduction and Phase Transformations at the Au-TiO2 Interface by Vibrational Spectroscopy(Bussum : Baltzer, 2017-8-17) Pougin, Anna; Lüken, Alexander; Klinkhammer, Christina; Hiltrop, Dennis; Kauer, Max; Tölle, Katharina; Havenith-Newen, Martina; Morgenstern, Karina; Grünert, Wolfgang; Muhler, Martin; Strunk, JenniferBy a combination of FT-NIR Raman spectroscopy, infrared spectroscopy of CO adsorption under ultrahigh vacuum conditions (UHV-IR) and Raman spectroscopy in the line scanning mode the formation of a reduced titania phase in a commercial Au/TiO2 catalyst and in freshly prepared Au/anatase catalysts was detected. The reduced phase, formed at the Au-TiO2 interface, can serve as nucleation point for the formation of stoichiometric rutile. TinO2n−1 Magnéli phases, structurally resembling the rutile phase, might be involved in this process. The formation of the reduced phase and the rutilization process is clearly linked to the presence of gold nanoparticles and it does not proceed under similar conditions with the pure titania sample. Phase transformations might be both thermally or light induced, however, the colloidal deposition synthesis of the Au/TiO2 catalysts is clearly ruled out as cause for the formation of the reduced phase.
- ItemAddressing the Reproducibility of Photocatalytic Carbon Dioxide Reduction(Weinheim : Wiley-VCH Verlag, 2019) Marx, Maximilian; Mele, Andrea; Spannenberg, Anke; Steinlechner, Christoph; Junge, Henrik; Schollhammer, Philippe; Beller, MatthiasReproducibility of photocatalytic reactions, especially when conducted on small scale for improved turnover numbers with in situ formed catalysts can prove challenging. Herein, we showcase the problematic reproducibility on the example of attractive photocatalytic CO2 reduction utilizing [FeFe] hydrogenase mimics. These Fe complexes, well-known for their application in proton reduction reactions, were combined with a heteroleptic Cu photosensitizer and produced CO/H2/HCO2H mixtures of variable constitution. However, the reactions indicated a poor reproducibility, even when conducted with well-defined complexes. Based on our experience, we make suggestions for scientists working in the field of photocatalysis on how to address and report the reproducibility of novel photocatalytic reaction protocols. In addition, we would like to highlight the importance of studying reproducibility of novel reaction protocols, especially in the fields of photocatalytic water splitting and CO2 reduction, where TONs are widely used as the comparable measure for catalytic activity. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemSynthesis of Single Atom Based Heterogeneous Platinum Catalysts: High Selectivity and Activity for Hydrosilylation Reactions(Washington, DC : ACS Publ., 2017) Cui, Xinjiang; Junge, Kathrin; Dai, Xingchao; Kreyenschulte, Carsten; Pohl, Marga-Martina; Wohlrab, Sebastian; Shi, Feng; Brückner, Angelika; Beller, MatthiasCatalytic hydrosilylation represents a straightforward and atom-efficient methodology for the creation of C-Si bonds. In general, the application of homogeneous platinum complexes prevails in industry and academia. Herein, we describe the first heterogeneous single atom catalysts (SACs), which are conveniently prepared by decorating alumina nanorods with platinum atoms. The resulting stable material efficiently catalyzes hydrosilylation of industrially relevant olefins with high TON (≈105). A variety of substrates is selectively hydrosilylated including compounds with sensitive reducible and other functional groups (N, B, F, Cl). The single atom based catalyst shows significantly higher activity compared to related Pt nanoparticles.
- ItemCooperative catalytic methoxycarbonylation of alkenes: Uncovering the role of palladium complexes with hemilabile ligands(Cambridge : RSC, 2018) Dong, Kaiwu; Sang, Rui; Wei, Zhihong; Liu, Jie; Dühren, Ricarda; Spannenberg, Anke; Jiao, Haijun; Neumann, Helfried; Jackstell, Ralf; Franke, Robert; Beller, MatthiasMechanistic studies of the catalyst [Pd2(dba)3/1,1′-bis(tert-butyl(pyridin-2-yl)phosphanyl)ferrocene, L2] for olefin alkoxycarbonylation reactions are described. X-ray crystallography reveals the coordination of the pyridyl nitrogen atom in L2 to the palladium center of the catalytic intermediates. DFT calculations on the elementary steps of the industrially relevant carbonylation of ethylene (the Lucite α-process) indicate that the protonated pyridyl moiety is formed immediately, which facilitates the formation of the active palladium hydride complex. The insertion of ethylene and CO into this intermediate leads to the corresponding palladium acyl species, which is kinetically reversible. Notably, this key species is stabilized by the hemilabile coordination of the pyridyl nitrogen atom in L2. The rate-determining alcoholysis of the acyl palladium complex is substantially facilitated by metal-ligand cooperation. Specifically, the deprotonation of the alcohol by the built-in base of the ligand allows a facile intramolecular nucleophilic attack on the acyl palladium species concertedly. Kinetic measurements support this mechanistic proposal and show that the rate of the carbonylation step is zero-order dependent on ethylene and CO. Comparing CH3OD and CH3OH as nucleophiles suggests the involvement of (de)protonation in the rate-determining step.
- ItemEnzyme Activity by Design: An Artificial Rhodium Hydroformylase for Linear Aldehydes(Weinheim : Wiley-VCH, 2017-9-13) Jarvis, Amanda G.; Obrecht, Lorenz; Deuss, Peter J.; Laan, Wouter; Gibson, Emma K.; Wells, Peter P.; Kamer, Paul C. J.Artificial metalloenzymes (ArMs) are hybrid catalysts that offer a unique opportunity to combine the superior performance of natural protein structures with the unnatural reactivity of transition-metal catalytic centers. Therefore, they provide the prospect of highly selective and active catalytic chemical conversions for which natural enzymes are unavailable. Herein, we show how by rationally combining robust site-specific phosphine bioconjugation methods and a lipid-binding protein (SCP-2L), an artificial rhodium hydroformylase was developed that displays remarkable activities and selectivities for the biphasic production of long-chain linear aldehydes under benign aqueous conditions. Overall, this study demonstrates that judiciously chosen protein-binding scaffolds can be adapted to obtain metalloenzymes that provide the reactivity of the introduced metal center combined with specifically intended product selectivity.
- Item3,3′-Dimethyl-1,1′-methylenediimidazolium tetrabromidocobaltate(II)(Chester : IUCr, 2018) Peppel, Tim; Spannenberg, AnkeThe title compound, (C9H14N4)[CoBr4], was obtained as single crystals directly in very low yield as a side product in the reaction of 1,1′-bis(1-methylimidazolium)acetate bromide and CoBr2. The title compound consists of an imidazolium-based dication and a tetrabromidocobaltate(II) complex anion, which are connected via C—H...Br interactions in the crystal. The dihedral angle between the imidazolium rings in the cation is 72.89 (16)°. The CoII ion in the anion is coordinated tetrahedrally by four bromide ligands [Co—Br = 2.4025 (5)–2.4091 (5) Å and Br—Co—Br = 106.224 (17)–113.893 (17)°]. The compound exhibits a high melting point (>300°C) and is a light-blue solid under ambient conditions.
- ItemSynthetic strategies to bicyclic tetraphosphanes using P1, P2 and P4 building blocks(London : Soc., 2015) Bresien, Jonas; Faust, Kirill; Hering-Junghans, Christian; Rothe, Julia; Schulz, Axel; Villinger, AlexanderDifferent reactions of Mes* substituted phosphanes (Mes* = 2,4,6-tri-tert-butylphenyl) led to the formation of the bicyclic tetraphosphane Mes*P4Mes* (5) and its unknown Lewis acid adduct 5·GaCl3. In this context, the endo–exo isomer of 5 was fully characterized for the first time. The synthesis was achieved by reactions involving “self-assembly” of the P4 scaffold from P1 building blocks (i.e. primary phosphanes) or by reactions starting from P2 or P4 scaffolds (i.e. a diphosphene or cyclic tetraphosphane). Furthermore, interconversion between the exo–exo and endo–exo isomer were studied by 31P NMR spectroscopy. All compounds were fully characterized by experimental as well as computational methods.
- ItemHydrogenation of Polyesters to Polyether Polyols(Weinheim : Wiley-VCH, 2019) Stadler, Bernhard M.; Hinze, Sandra; Tin, Sergey; de Vries, Johannes G.The amount of plastic waste is continuously increasing. Besides conventional recycling, one solution to deal with this problem could be to use this waste as a resource for novel materials. In this study, polyesters are hydrogenated to give polyether polyols by using in situ-generated Ru-Triphos catalysts in combination with Lewis acids. The choice of Lewis acid and its concentration relative to the ruthenium catalyst are found to determine the selectivity of the reaction. Monitoring of the molecular weight during the reaction confirms a sequential mechanism in which the diols that are formed by hydrogenation are etherified to the polyethers. To probe the applicability of this tandem hydrogenation etherification approach, a range of polyester substrates is investigated. The oligoether products that form in these reactions have the chain lengths that are appropriate for application in the adhesives and coatings industries. This strategy makes polyether polyols accessible that are otherwise difficult to obtain from conventional fossil-based feedstocks. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemCrystal structure of 1-bis(((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl) cyclopentadienyl)-1-trimethylphosphine-2,3-bis(trimethylsilyl) -1-hafnacycloprop-2-ene-hexane (1:0.5), (HfC8H18Si 2)(C15H22)2(PC3H 9) · 0.5C6H14(Berlin : de Gruyter, 2010) Klahn, M.; Spannenberg, A.; Rosenthal, U.C44H78HfPSi2, tetragonal, P4 1212 (no. 92), a = 14.9634(2) Å, c = 44.9270(8) Å, V = 10059.3 Å3, Z = 8, Rgt(F) = 0.026, wRref(F2) = 0.073, T = 200 K. © by Oldenbourg Wissenschaftsverlag, München.
- ItemProperties of Novel Polyesters Made from Renewable 1,4-Pentanediol(Weinheim : Wiley-VCH, 2019) Stadler, Bernhard M.; Brandt, Adrian; Kux, Alexander; Beck, Horst; de Vries, Johannes G.Novel polyester polyols were prepared in high yields from biobased 1,4-pentanediol catalyzed by non-toxic phosphoric acid without using a solvent. These oligomers are terminated with hydroxyl groups and have low residual acid content, making them suitable for use in adhesives by polyurethane formation. The thermal behavior of the polyols was studied by differential scanning calorimetry, and tensile testing was performed on the derived polyurethanes. The results were compared with those of polyurethanes obtained with fossil-based 1,4-butanediol polyester polyols. Surprisingly, it was found that a crystalline polyester was obtained when aliphatic long-chain diacids (>C12) were used as the diacid building block. The low melting point of the C12 diacid-based material allows the development of biobased shape-memory polymers with very low switching temperatures (<0 °C), an effect that has not yet been reported for a material based on a simple binary polyester. This might find application as thermosensitive adhesives in the packaging of temperature-sensitive goods such as pharmaceuticals. Furthermore, these results indicate that, although 1,4-pentanediol cannot be regarded as a direct substitute for 1,4-butanediol, its novel structure expands the toolbox of the adhesives, coatings, or sealants formulators. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.