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- ItemIntermolecular hydrogen bonding in isostructural pincer complexes [OH-(t-BuPOCOPt-Bu)MCl] (M = Pd and Pt)(Chester : International Union of Crystallography, 2019) Joksch, M.; Spannenberg, A.; Beweries, T.In the crystal structure of the isostructural title compounds, namely {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridopalladium(II), [Pd(C22H39O3P2)Cl], 1, and {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridoplatinum(II), [Pt(C22H39O3P2)Cl], 2, the metal centres are coordinated in a distorted square-planar fashion by the POCOP pincer fragment and the chloride ligand. Both complexes form strong hydrogen-bonded chain structures through an interaction of the OH group in the 4-position of the aromatic POCOP backbone with the halide ligand.
- ItemHydrogen Bonding Between Ions of Like Charge in Ionic Liquids Characterized by NMR Deuteron Quadrupole Coupling Constants—Comparison with Salt Bridges and Molecular Systems(Weinheim : Wiley-VCH, 2019) Khudozhitkov, Alexander E.; Neumann, Jan; Niemann, Thomas; Zaitsau, Dzmitry; Stange, Peter; Paschek, Dietmar; Stepanov, Alexander G.; Kolokolov, Daniil I.; Ludwig, RalfWe present deuteron quadrupole coupling constants (DQCC) for hydroxyl-functionalized ionic liquids (ILs) in the crystalline or glassy states characterizing two types of hydrogen bonding: The regular Coulomb-enhanced hydrogen bonds between cation and anion (c–a), and the unusual hydrogen bonds between cation and cation (c–c), which are present despite repulsive Coulomb forces. We measure these sensitive probes of hydrogen bonding by means of solid-state NMR spectroscopy. The DQCCs of (c–a) ion pairs and (c–c) H-bonds are compared to those of salt bridges in supramolecular complexes and those present in molecular liquids. At low temperatures, the (c–c) species successfully compete with the (c–a) ion pairs and dominate the cluster populations. Equilibrium constants obtained from molecular-dynamics (MD) simulations show van't Hoff behavior with small transition enthalpies between the differently H-bonded species. We show that cationic-cluster formation prevents these ILs from crystallizing. With cooling, the (c–c) hydrogen bonds persist, resulting in supercooling and glass formation. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemActivation, deactivation and reversibility phenomena in homogeneous catalysis : A showcase based on the chemistry of rhodium/phosphine catalysts(Basel : MDPI, 2019) Alberico, Elisabetta; Möller, Saskia; Horstmann, Moritz; Drexler, Hans-Joachim; Heller, DetlefIn the present work, the rich chemistry of rhodium/phosphine complexes, which are applied as homogeneous catalysts to promote a wide range of chemical transformations, has been used to showcase how the in situ generation of precatalysts, the conversion of precatalysts into the actually active species, as well as the reaction of the catalyst itself with other components in the reaction medium (substrates, solvents, additives) can lead to a number of deactivation phenomena and thus impact the efficiency of a catalytic process. Such phenomena may go unnoticed or may be overlooked, thus preventing the full understanding of the catalytic process which is a prerequisite for its optimization. Based on recent findings both from others and the authors’ laboratory concerning the chemistry of rhodium/diphosphine complexes, some guidelines are provided for the optimal generation of the catalytic active species from a suitable rhodium precursor and the diphosphine of interest; for the choice of the best solvent to prevent aggregation of coordinatively unsaturated metal fragments and sequestration of the active metal through too strong metal–solvent interactions; for preventing catalyst poisoning due to irreversible reaction with the product of the catalytic process or impurities present in the substrate. © 2019 by the authors.
- ItemCobalt pincer complexes for catalytic reduction of nitriles to primary amines(London : RSC Publ., 2019) Schneekönig, Jacob; Tannert, Bianca; Hornke, Helen; Beller, Matthias; Junge, KathrinVarious cobalt pincer type complexes 1-6 were applied for the catalytic hydrogenation of nitriles to amines. Among these, catalyst 4 is the most efficient, allowing the reduction of aromatic as well as aliphatic nitriles in moderate to excellent yields. © 2019 The Royal Society of Chemistry.
- ItemRice husk derived porous silica as support for pd and CeO2 for low temperature catalytic methane combustion(Basel : MDPI, 2019) Liu, Dongjing; Seeburg, Dominik; Kreft, Stefanie; Bindig, René; Hartmann, Ingo; Schneider, Denise; Enke, Dirk; Wohlrab, SebastianThe separation of Pd and CeO2 on the inner surface of controlled porous glass (CPG, obtained from phase-separated borosilicate glass after extraction) yields long-term stable and highly active methane combustion catalysts. However, the limited availability of the CPG makes such catalysts highly expensive and limits their applicability. In this work, porous silica obtained from acid leached rice husks after calcination (RHS) was used as a sustainable, cheap and broadly available substitute for the above mentioned CPG. RHS-supported Pd-CeO2 with separated CeO2 clusters and Pd nanoparticles was fabricated via subsequent impregnation/calcination of molten cerium nitrate and different amounts of palladium nitrate solution. The Pd/CeO2/RHS catalysts were employed for the catalytic methane combustion in the temperature range of 150–500◦C under methane lean conditions (1000 ppm) in a simulated off-gas consisting of 9.0 vol% O2, and 5.5 vol% CO2 balanced with N2. Additionally, tests with 10.5 vol% H2O as co-feed were carried out. The results revealed that the RHS-supported catalysts reached the performance of the cost intensive benchmark catalyst based on CPG. The incorporation of Pd-CeO2 into RHS additionally improved water-resistance compared to solely Pd/CeO2 lowering the required temperature for methane combustion in presence of 10.5 vol% H2O to values significantly below 500◦C (T90 = 425◦C). © 2019 by the authors. Licensee MDPI, Basel, Switzerland.
- 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.
- ItemCorrection: Increasing steric demand through flexible bulk – primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones(London : Soc., 2019) Bresien, Jonas; Goicoechea, Jose M.; Hinz, Alexander; Scharnhölz, Moritz T.; Schulz, Axel; Suhrbier, Tim; Villinger, AlexanderCorrection for 'Increasing steric demand through flexible bulk-primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones' by Jonas Bresien et al., Dalton Trans., 2019, 48, 3786-3794. © 2019 The Royal Society of Chemistry.
- 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.
- ItemPNPN-H in Comparison to other PNP, PNPN and NPNPN Ligands for the Chromium Catalyzed Selective Ethylene Oligomerization(Weinheim : Wiley-VCH Verlag, 2019) Rosenthal, UweMany examples exist for the chromium catalyzed selective ethylene oligomerization in which the influence of ligands is essential for the formation of products. Regarding the tri- and tetramerization to 1-hexene or 1-octene mostly PNP ligands are responsible for the tetra- and some of such modified ligands for the trimerization. A very special case in these reactions are PNPN−H ligands, showing in most cases highly selective trimerization of ethylene to 1-hexene. In this review all existing published information about these PNPN−H ligands is accumulated and compared to some other related PNP, PNPN and NPNPN ligands in the chromium catalyzed selective ethylene oligomerization with respect to the switch from tetra- to trimerization and back by different substituent pattern of PNP ligand. Mechanistic information and arguments are collected to explain the switch from tetra- to trimerization and back by substitution of functional groups in classical PNP to PNPN−H ligands as a result of mono- and dinuclear catalytic species. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemEffects of substitution pattern in phosphite ligands used in rhodium-catalyzed hydroformylation on reactivity and hydrolysis stability(Basel : MDPI, 2019) Kloß, Svenja; Selent, Detlef; Spannenberg, Anke; Franke, Robert; Börner, Armin; Sharif, MuhammadThe stability of homogeneous catalytic systems is an industrially crucial topic, which, however, receives comparatively little attention from academic research. Phosphites are among the most frequently used ligands in industrial, rhodium-catalyzed n-regioselective hydroformylation. However, they are particularly vulnerable to hydrolysis. Since the decomposition of ligands should be dependent on the substitution patterns, phenyl, tert-butyl and condensed ring systems of benzopinacolphosphites were evaluated concerning their activity, regioselectivity and hydrolysis stability. A series of twelve strongly related phosphites were synthesized, tested in the hydroformylation of isomeric n-octenes, and studied in hydrolysis experiments using in situ NMR spectroscopy. Our results show that substituents in the ortho-position, especially tert-butyl substituents, enhance hydrolysis stability while maintaining compelling activity and regioselectivity. In contrast, substituents in the para-position may destabilize the phosphite. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.