03 Fakultät Chemie

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Institute: search.filters.UBSInstitut.Institut für Theoretische ChemiePublication Type: search.filters.UBSTyp.Zeitschriftenartikel

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    Highly active cooperative Lewis acid : ammonium salt catalyst for the enantioselective hydroboration of ketones
    (2021) Titze, Marvin; Heitkämper, Juliane; Junge, Thorsten; Kästner, Johannes; Peters, René
    Enantiopure secondary alcohols are fundamental high‐value synthetic building blocks. One of the most attractive ways to get access to this compound class is the catalytic hydroboration. We describe a new concept for this reaction type that allowed for exceptional catalytic turnover numbers (up to 15 400), which were increased by around 1.5-3 orders of magnitude compared to the most active catalysts previously reported. In our concept an aprotic ammonium halide moiety cooperates with an oxophilic Lewis acid within the same catalyst molecule. Control experiments reveal that both catalytic centers are essential for the observed activity. Kinetic, spectroscopic and computational studies show that the hydride transfer is rate limiting and proceeds via a concerted mechanism, in which hydride at Boron is continuously displaced by iodide, reminiscent to an SN2 reaction. The catalyst, which is accessible in high yields in few steps, was found to be stable during catalysis, readily recyclable and could be reused 10 times still efficiently working.
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    Field evaporation and atom probe tomography of pure water tips
    (2020) Schwarz, T. M.; Weikum, E. M.; Meng, K.; Hadjixenophontos, E.; Dietrich, C. A.; Kästner, J.; Stender, P.; Schmitz, G.
    Measuring biological samples by atom probe tomography (APT) in their natural environment, i.e. aqueous solution, would take this analytical method, which is currently well established for metals, semi-conductive materials and non-metals, to a new level. It would give information about the 3D chemical structure of biological systems, which could enable unprecedented insights into biological systems and processes, such as virus protein interactions. For this future aim, we present as a first essential step the APT analysis of pure water (Milli-Q) which is the main component of biological systems. After Cryo-preparation, nanometric water tips are field evaporated with assistance by short laser pulses. The obtained data sets of several tens of millions of atoms reveal a complex evaporation behavior. Understanding the field evaporation process of water is fundamental for the measurement of more complex biological systems. For the identification of the individual signals in the mass spectrum, DFT calculations were performed to prove the stability of the detected molecules.
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    Spectroscopic characterization of diazophosphane - a candidate for astrophysical observations
    (2023) Tschöpe, Martin; Rauhut, Guntram
    Quite recently, diazophosphane, HP-N≡N, was synthesized for the first time. This was accomplished by a reaction of PH3 with N2 under UV irradiation at 193 nm. As these two molecules have been observed in different astrophysical environments, as for example, in the circumstellar medium and, in particular, in the AGB star envelope IRC+10216, the question arises whether HPN2 can be found as well. So far there is only the aforementioned experimental work, but neither rotational nor rovibrational data are available. Hence, the lack of accurate line lists, etc. to identify diazophosphane is the subject of this work, including a detailed analysis of the rotational, vibrational, and rovibrational properties for this molecule. Our calculations rely on multidimensional potential energy surfaces obtained from explicitly correlated coupled-cluster theory. The (ro)vibrational calculations are based on related configuration interaction theories avoiding the need for any model Hamiltonians. The rotational spectrum is studied between T = 10 and 300 K. In contrast, the partition functions for HPN2 and DPN2 are given and compared for temperatures up to 800 K. In addition, more than 70 vibrational transitions are calculated and analyzed with respect to resonances. All these vibrational states are considered within the subsequent rovibrational calculations. This allows for a detailed investigation of the infrared spectrum up to 2700 cm-1 including rovibrational couplings and hot bands. The results of this study serve as a reference and allow, for the first time, for the identification of diazophosphane, for example, in one of the astrophysical environments mentioned above.
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    Use of time domain nuclear magnetic resonance relaxometry to monitor the effect of magnetic field on the copper corrosion rate in real time
    (2022) Igreja Nascimento Mitre, Cirlei; Ferreira Gomes, Bruna; Paris, Elaine; Silva Lobo, Carlos Manuel; Roth, Christina; Colnago, Luiz Alberto
    The corrosion of metals is a major problem of modern societies, demanding new technologies and studies to understand and minimize it. Here we evaluated the effect of a magnetic field (B) on the corrosion of copper in aqueous HCl solution under open circuit potential. The corrosion product, Cu2+, is a paramagnetic ion and its concentration in the solution was determined in real time in the corrosion cell by time-domain NMR relaxometry. The results show that the magnetic field (B = 0.23 T) of the time-domain NMR instrument reduces the corrosion rate by almost 50%, in comparison to when the corrosion reaction is performed in the absence of B. Atomic force microscopy and X-ray diffraction results of the analysis of the corroded surfaces reveal a detectable CuCl phase and an altered morphology when B is present. The protective effect of B was explained by magnetic forces that maintain the Cu2+ in the solution/metal interface for a longer time, hindering the arrival of the new corrosive agents, and leading to the formation of a CuCl phase, which may contribute to the rougher surface. The time-domain NMR method proved to be useful to study the effect of B in the corrosion of other metals or other corrosive liquid media when the reactions produce or consume paramagnetic ions.
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    The reactivity of pyridine in cold interstellar environments : the reaction of pyridine with the CN radical
    (2022) Heitkämper, Juliane; Suchaneck, Sarah; García de la Concepción, Juan; Kästner, Johannes; Molpeceres, Germán
    The recent detection of cyclic species in cold interstellar environments is an exciting discovery with yet many unknowns to be solved. Among them, the presence of aromatic heterocycles in space would act as an indirect evidence of the presence of precursors of nucleotides. The seeming absence of these species in the observations poses a fascinating conundrum that can be tackled with computational insights. Whilst many arguments can be given to explain the absence of heterocycles in space, one of the possible scenarios involves fast chemical conversion and formation of new species to be detected. We have tested this hypothesis for the reaction of pyridine with the CN radical to find possible scenarios in which the detectability of pyridine, as an archetypical heterocycle, could be enhanced or diminished via chemical conversions. Using a combination of ab-initio characterization of the reactive potential energy surface and kinetic and chemical simulations, we have established that pyridine does react very fast with CN radicals, estimating that the studied reactions is between 2.5-4.5 times faster in pyridine than in benzene, with a total loss rate constant of 1.33 × 10-9 cm3s-1 at 30 K, with an almost null temperature dependence in the (30-150) K range. Addition reactions forming 1,2,3-cyanopyridine are favored over abstraction reactions or the formation of isocyanides. Besides, for 1 and 2-cyanopyridine there is an increase in the total dipole moment with respect to pyridine, which can help in their detection. However, the reaction is not site specific, and equal amounts of 1,2,3-cyanopyridine are formed during the reaction, diluting the abundance of all the individual pyridine derivatives.
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    Are different stoichiometries feasible for complexes between lymphotoxin-alpha and tumor necrosis factor receptor 1?
    (2012) Mascarenhas, Nahren Manuel; Kästner, Johannes
    Background Tumor necrosis factors, TNF and lymphotoxin-α (LT), are cytokines that bind to two receptors, TNFR1 and TNFR2 (TNF-receptor 1 and 2) to trigger their signaling cascades. The exact mechanism of ligand-induced receptor activation is still unclear. It is generally assumed that three receptors bind to the homotrimeric ligand to trigger a signaling event. Recent evidence, though, has raised doubts if the ligand:receptor stoichiometry should indeed be 3:3 for ligand-induced cellular response. We used molecular dynamics simulations, elastic network models, as well as MM/PBSA to analyze this question. Results Applying MM/PBSA methodology to different stoichiometric complexes of human LT-(TNFR1)n=1,2,3 the free energy of binding in these complexes has been estimated by single-trajectory and separate-trajectory methods. Simulation studies rationalized the favorable binding energy in the LT-(TNFR1)1 complex, as evaluated from single-trajectory analysis to be an outcome of the interaction of cysteine-rich domain 4 (CRD4) and the ligand. Elastic network models (ENMs) help to associate the difference in the global fluctuation of the receptors in these complexes. Functionally relevant transformation associated with these complexes reveal the difference in the dynamics of the receptor when free and in complex with LT. Conclusions MM/PBSA predicts complexes with a ligand-receptor molar ratio of 3:1 and 3:2 to be energetically favorable. The high affinity associated with LT-(TNFR1)1 is due to the interaction between the CRD4 domain with LT. The global dynamics ascertained from ENMs have highlighted the differential dynamics of the receptor in different states.
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    Structural characterization of surface immobilized platinum hydrides by sensitivity-enhanced 195Pt solid state NMR spectroscopy and DFT calculations
    (2024) Atterberry, Benjamin A.; Wimmer, Erik J.; Klostermann, Sina; Frey, Wolfgang; Kästner, Johannes; Estes, Deven P.; Rossini, Aaron J.
    Supported single-site platinum hydride compounds are promising heterogeneous catalysts for organic transformations. Few methods exist to describe the structures of single-site Pt catalysts with atomic resolution because of their disordered structures and low Pt loadings. Here, we study the compounds formed when bis(tri-tert-butylphosphino)platinum, Pt(PtBu3)2, is supported on dehydroxylated SiO2 or SiO2-Al2O3. First, we obtain magic angle spinning (MAS) 1H, 31P and 195Pt ssNMR spectra of four model Pt phosphine compounds with oxidation states of 0 or +2 and coordination numbers between 2 and 4. These compounds are analogs of potential structures present in the supported compounds. MAS 195Pt ssNMR spectra were obtained using 31P{195Pt} sideband selective J-resolved and J-HMQC experiments. The measured 1H and 31P chemical shifts, 31P-195Pt J-couplings and 195Pt chemical shift (CS) tensors are shown to be diagnostic of oxidation state and coordination number. Room temperature 1H ssNMR spectra of Pt(PtBu3)2 supported on SiO2 or SiO2-Al2O3 show diagnostic hydride NMR signals, suggesting that Pt(PtBu3)2 undergoes oxidative addition, resulting in surface hydrides and Pt–oxygen bonds to the support surface. MAS dynamic nuclear polarization (DNP) enables 31P{195Pt} correlation NMR experiments on the supported compounds. These experiments enable the measurement of the 31P-195Pt J-coupling constants and 195Pt CS tensors. Combined NMR and DFT analyses suggest that the primary surface platinum species are [HPt(PtBu3)2OSi] on SiO2 and [HPt(PtBu3)2]+[Si-O--Al] on SiO2-Al2O3. The Pt-oxygen bond length is dependent on the support and estimated as 2.1-2.3 Å and 2.7-3.0 Å for SiO2 and SiO2-Al2O3, respectively.
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    Sulfur‐composites derived from poly(acrylonitrile) and poly(vinylacetylene) : a comparative study on the role of pyridinic and thioamidic nitrogen
    (2023) Kappler, Julian; Klostermann, Sina V.; Lange, Pia L.; Dyballa, Michael; Veith, Lothar; Schleid, Thomas; Weil, Tanja; Kästner, Johannes; Buchmeiser, Michael R.
    Sulfurized poly(acrylonitrile) (SPAN) is a prominent example of a highly cycle stable and rate capable sulfur/polymer composite, which is solely based on covalently bound sulfur. However, so far no in‐depth study on the influence of nitrogen in the carbonaceous backbone, to which sulfur in the form of thioketones and poly(sulfides) is attached, exists. Herein, we investigated the role of nitrogen by comparing sulfur/polymer composites derived from nitrogen‐containing poly(acrylonitrile) (PAN) and nitrogen‐free poly(vinylacetylene) (PVac). Results strongly indicate the importance of a nitrogen‐rich, aromatic carbon backbone to ensure full addressability of the polymer‐bound sulfur and its reversible binding to the aromatic backbone, even at high current rates. This study also presents key structures, which are crucial for highly cycle and rate stable S‐composites.
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    Oxo‐bridged Zr dimers as well‐defined models of oxygen vacancies on ZrO2
    (2023) Wimmer, Erik J.; Klostermann, Sina V.; Ringenberg, Mark; Kästner, Johannes; Estes, Deven P.
    While ZrO2 is known to have a large effect on the activity and selectivity of the Cu/ZrO2 catalyst for methanol synthesis, its role in this process is poorly understood. Surface defects such as oxygen vacancies could play a role in the strong metal-support interaction (SMSI) between Cu and ZrO2. However, due to the complexity of the surfaces, the exact molecular nature of this interaction is not at present known. Here, we make well-defined models of both reduced and coordinatively unsaturated surface oxygen vacancies on ZrO2 using the molecular precursor [Cp2ZrCl]2(μ2-O) (1). Complex 1 can be reduced to form a complex (2) containing one Zr(III) center and a bridging hydride ligand (according to EPR and IR spectroscopy) derived from C-H activation of either thf or the Cp ring. Complex 2 reacts with CO2 to largely produce CO, suggesting that surface defects with similar structures probably do not play a role in the industrial catalyst. Halide abstraction from complex 1 results in the Lewis acidic species 3, which has similar Lewis acid properties to acidic defects on the ZrO2 surface. Similarities of both of these model species to real surface oxygen vacancies and their role in the catalytic reaction are discussed.
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    The quasi-binary acetonitriletriide Sr3[C2N]2
    (2019) Clark, William P.; Köhn, Andreas; Niewa, Rainer
    The first quasi-binary acetonitriletriide Sr3[C2N]2 has been synthesised and characterised. The nearly colourless crystals were obtained from the reaction of Sr metal, graphite, and elemental N2, generated by decomposition of Sr(N3)2, in a sealed Ni ampoule with the aid of an alkali metal flux. The structure of this compound was analysed via single-crystal Xray diffraction and the identity of the [C2N]3- anion was confirmed by Raman spectroscopy and further investigated by quantum-chemical methods. Computed interatomic distances within the [C2N]3- anion strikingly match the obtained experimental data.