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- ItemOn the Reactivity of Phosphaalumenes towards C−C Multiple Bonds(Weinheim : Wiley-VCH, 2023) Nees, Samuel; Wellnitz, Tim; Dankert, Fabian; Härterich, Marcel; Dotzauer, Simon; Feldt, Milica; Braunschweig, Holger; Hering‐Junghans, ChristianHeterocycles containing group 13 and 15 elements such as borazines are an integral part of organic, biomedical and materials chemistry. Surprisingly, heterocycles containing P and Al are rare. We have now utilized phosphaalumenes in reactions with alkynes, alkenes and conjugated double bond systems. With sterically demanding alkynes 1,2-phosphaalumetes were afforded, whereas the reaction with HCCH or HCCSiMe3 gave 1,4-phosphaaluminabarrelenes. Using styrene saturated 1,2-phosphaalumates were formed, which reacted further with additional styrene to give different regio-isomers of 1,4-aluminaphosphorinanes. Using ethylene, a 1,4-aluminaphosphorinane is obtained, while with 1,3-butadiene a bicyclic system containing an aluminacyclopentane and a phosphirane unit was synthesized. The experimental work is supported by theoretical studies to shed light on the mechanism governing the formation of these heterocycles.
- 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.
- ItemA Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol(Weinheim : Wiley-VCH, 2016-12-2) Andérez-Fernández, María; Vogt, Lydia K.; Fischer, Steffen; Zhou, Wei; Jiao, Haijun; Garbe, Marcel; Elangovan, Saravanakumar; Junge, Kathrin; Junge, Henrik; Ludwig, Ralf; Beller, MatthiasFor the first time, structurally defined manganese pincer complexes catalyze the dehydrogenation of aqueous methanol to hydrogen and carbon dioxide, which is a transformation of interest with regard to the implementation of a hydrogen and methanol economy. Excellent long-term stability was demonstrated for the Mn-PNPiPr catalyst, as a turnover of more than 20 000 was reached. In addition to methanol, other important hydrogen carriers were also successfully dehydrogenated.
- ItemSynthesis and crystallographic characterization of [2,2-bis(η5-pentamethylcyclopentadienyl)-3,4-bis(trimethylsilyl)-2-zirconafuran-5-one-κO5]triisobutylaluminium(Chester : International Union of Crystallography, 2018-3-27) Burlakov, Vladimir V.; Bogdanov, Vyacheslav S.; Arndt, Perdita; Spannenberg, Anke; Rosenthal, Uwe; Beweries, Torsten; Shur, Vladimir B.The crystal structure of the title zwitterionic zirconocene complex containing a furanone unit, [AlZr(C10H15)2(C4H9)3(C9H18O2Si2)], is reported. On reacting a zirconafuranone with two equivalents of HAl(i-Bu)2, disproportionation of the Lewis acid results in the formation of a triisobutylaluminium fragment, Al(i-Bu)3, which coordinates to the exocyclic carbonyl O atom of the zirconafuranone ring. Single-crystal X-ray diffraction reveals that the zirconafuranone ring remains intact with coordination of the aluminium to the exocyclic O atom. One of the i-butyl groups is disordered over two sets of sites, with an occupancy ratio of 0.731 (3):0.269 (3).
- 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.
- ItemUnraveling the H2 Promotional Effect on Palladium-Catalyzed CO Oxidation Using a Combination of Temporally and Spatially Resolved Investigations(Washington, DC : ACS, 2018) Stewart, Caomhán; Gibson, Emma K.; Morgan, Kevin; Cibin, Giannantonio; Dent, Andrew J.; Hardacre, Christopher; Kondratenko, Evgenii V.; Kondratenko, Vita A.; McManus, Colin; Rogers, Scott; Stere, Cristina E.; Chansai, Sarayute; Wang, Yi-Chi; Haigh, Sarah J.; Wells, Peter P.; Goguet, AlexandreThe promotional effect of H2 on the oxidation of CO is of topical interest, and there is debate over whether this promotion is due to either thermal or chemical effects. As yet there is no definitive consensus in the literature. Combining spatially resolved mass spectrometry and X-ray absorption spectroscopy (XAS), we observe a specific environment of the active catalyst during CO oxidation, having the same specific local coordination of the Pd in both the absence and presence of H2. In combination with Temporal Analysis of Products (TAP), performed under isothermal conditions, a mechanistic insight into the promotional effect of H2 was found, providing clear evidence of nonthermal effects in the hydrogen-promoted oxidation of carbon monoxide. We have identified that H2 promotes the Langmuir-Hinshelwood mechanism, and we propose this is linked to the increased interaction of O with the Pd surface in the presence of H2. This combination of spatially resolved MS and XAS and TAP studies has provided previously unobserved insights into the nature of this promotional effect.
- ItemToward Green Acylation of (Hetero)arenes: Palladium-Catalyzed Carbonylation of Olefins to Ketones(Washington, DC : ACS Publ., 2017) Liu, Jie; Wei, Zhihong; Jiao, Haijun; Jackstell, Ralf; Beller, MatthiasGreen Friedel-Crafts acylation reactions belong to the most desired transformations in organic chemistry. The resulting ketones constitute important intermediates, building blocks, and functional molecules in organic synthesis as well as for the chemical industry. Over the past 60 years, advances in this topic have focused on how to make this reaction more economically and environmentally friendly by using green acylating conditions, such as stoichiometric acylations and catalytic homogeneous and heterogeneous acylations. However, currently well-established methodologies for their synthesis either produce significant amounts of waste or proceed under harsh conditions, limiting applications. Here, we present a new protocol for the straightforward and selective introduction of acyl groups into (hetero)arenes without directing groups by using available olefins with inexpensive CO. In the presence of commercial palladium catalysts, inter- and intramolecular carbonylative C-H functionalizations take place with good regio- and chemoselectivity. Compared to classical Friedel-Crafts chemistry, this novel methodology proceeds under mild reaction conditions. The general applicability of this methodology is demonstrated by the direct carbonylation of industrial feedstocks (ethylene and diisobutene) as well as of natural products (eugenol and safrole). Furthermore, synthetic applications to drug molecules are showcased.
- ItemForty years of temporal analysis of products(London : RSC Publ., 2017) Morgan, K.; Maguire, N.; Fushimi, R.; Gleaves, J. T.; Goguet, A.; Harold, M. P.; Kondratenko, E. V.; Menon, U.; Schuurman, Y.; Yablonsky, G. S.A detailed understanding of reaction mechanisms and kinetics is required in order to develop and optimize catalysts and catalytic processes. While steady-state investigations are known to give a global view of the catalytic system, transient studies are invaluable since they can provide more comprehensive insight into elementary steps. For almost forty years temporal analysis of products (TAP) has been successfully utilized for transient studies of gas phase heterogeneous reactions, and there have been a number of advances in instrumentation and numerical modeling methods in that time. Since TAP is a complex methodology it is often viewed as a niche specialty. With the purpose to make TAP more relevant and approachable to a wider segment of the catalytic research community, part of the intention of this work is to highlight the significant contributions TAP has made to elucidating mechanistic and kinetic aspects of complex, multi-step heterogeneous reactions. With this in mind, an outlook is also disclosed for the technique in terms of what is needed to revitalize the field and make it more applicable to the recent advances in catalyst characterization (e.g. operando modes).
- ItemRelations between Structure, Activity and Stability in C3N4 Based Photocatalysts Used for Solar Hydrogen Production(Basel : MDPI, 2018-1-29) Sivasankaran, Ramesh P.; Rockstroh, Nils; Hollmann, Dirk; Kreyenschulte, Carsten R.; Agostini, Giovanni; Lund, Henrik; Acharjya, Amitava; Rabeah, Jabor; Bentrup, Ursula; Junge, Henrik; Thomas, Arne; Brückner, AngelikaSolar hydrogen production from water could be a sustainable and environmentally friendly alternative to fossil energy carriers, yet so far photocatalysts active and stable enough for large-scale applications are not available, calling for advanced research efforts. In this work, H2 evolution rates of up to 1968 and 5188 μmol h−1 g−1 were obtained from aqueous solutions of triethanolamine (TEOA) and oxalic acid (OA), respectively, by irradiating composites of AgIn5S8 (AIS), mesoporous C3N4 (CN, surface area >150 m2/g) and ≤2 wt.% in-situ photodeposited Pt nanoparticles (NPs) with UV-vis (≥300 nm) and pure visible light (≥420 nm). Structural properties and electron transport in these materials were analyzed by XRD, STEM-HAADF, XPS, UV-vis-DRS, ATR-IR, photoluminescence and in situ-EPR spectroscopy. Initial H2 formation rates were highest for Pt/CN, yet with TEOA this catalyst deactivated by inclusion of Pt NPs in the matrix of CN (most pronounced at λ ≥ 300 nm) while it remained active with OA, since in this case Pt NPs were enriched on the outermost surface of CN. In Pt/AIS-CN catalysts, Pt NPs were preferentially deposited on the surface of the AIS phase which prevents them from inclusion in the CN phase but reduces simultaneously the initial H2 evolution rate. This suggests that AIS hinders transport of separated electrons from the CN conduction band to Pt NPs but retains the latter accessible by protons to produce H2.
- ItemCriticial Assessment of the Photocatalytic Reduction of Cr(VI) over Au/TiO2(Basel : MDPI, 2018-12-3) Ngo, Anh Binh; Nguyen, Hong Lien; Hollmann, DirkThe purification of drinking water is one of the most urgent challenges in developing countries, for which the efficient removal of traces of heavy metals, e.g., Cr(IV), represents a key technology. This can be achieved via photocatalysis. In this study, we compare the performance of Au/TiO2 to bare TiO2 P25 catalysts. Furthermore, the influence of the sacrificial reagent citric acid under UV-Vis and Vis excitation was investigated and a detailed investigation of the catalysts before and after reaction was performed. During the photocatalytic reduction of Cr(IV) under acidic conditions, both leaching of Au, as well as absorption of Cr, occur, resulting in new catalyst systems obtained in situ.