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- 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.
- 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.
- ItemSpectroscopic Evidence for Clusters of Like-Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding(Weinheim : Wiley-VCH, 2016) Knorr, Anne; Stange, Peter; Fumino, Koichi; Weinhold, Frank; Ludwig, RalfInfrared spectroscopy and density functional theory calculations provide strong evidence for the formation of clusters of like-charged ions in ionic liquids. With decreasing temperature, cooperative hydrogen bonding overcomes repulsive electrostatic interaction. The resulting cyclic tetramers nicely resemble well-known molecular clusters of alcohols.
- ItemHighly active and selective photochemical reduction of CO2 to CO using molecular-defined cyclopentadienone iron complexes(Cambridge : Soc., 2015) Rosas-Hernández, Alonso; Alsabeh, Pamela G.; Barsch, Enrico; Junge, Hernrik; Ludwig, Ralf; Beller, MatthiasHerein, we report highly active (cyclopentadienone)iron–tricarbonyl complexes for CO2 photoreduction using visible light with an Ir complex as photosensitizer and TEOA as electron/proton donor. Turnover numbers (TON) of ca. 600 (1 h) with initial turnover frequencies (TOF) up to 22.2 min−1 were observed. Operando FTIR measurements allowed for the proposal of a plausible mechanism for catalyst activation.
- ItemHydrogen bonding in a mixture of protic ionic liquids: A molecular dynamics simulation study(Cambridge : RSC Publ., 2015) Paschek, Dietmar; Golub, Benjamin; Ludwig, RalfWe report results of molecular dynamics (MD) simulations characterising the hydrogen bonding in mixtures of two different protic ionic liquids sharing the same cation: triethylammonium-methylsulfonate (TEAMS) and triethylammonium-triflate (TEATF). The triethylammonium-cation acts as a hydrogen-bond donor, being able to donate a single hydrogen-bond. Both, the methylsulfonate- and the triflate-anions can act as hydrogen-bond acceptors, which can accept multiple hydrogen bonds via their respective SO3-groups. In addition, replacing a methyl-group in the methylsulfonate by a trifluoromethyl-group in the triflate significantly weakens the strength of a hydrogen bond from an adjacent triethylammonium cation to the oxygen-site in the SO3-group of the anion. Our MD simulations show that these subtle differences in hydrogen bond strength significantly affect the formation of differently-sized hydrogen-bonded aggregates in these mixtures as a function of the mixture-composition. Moreover, the reported hydrogen-bonded cluster sizes can be predicted and explained by a simple combinatorial lattice model, based on the approximate coordination number of the ions, and using statistical weights that mostly account for the fact that each anion can only accept three hydrogen bonds.
- ItemThe effect of dispersion forces on the interaction energies and far infrared spectra of protic ionic liquids(Cambridge : RSC Publ., 2015) Ludwig, RalfWe could show by means of dispersion-corrected DFT calculations that the interaction energy in protic ionic liquids can be dissected into Coulomb interaction, hydrogen bonding and dispersion interaction. The H-bond energy as well as the dispersion energy can be quantified to be 50 kJ mol−1 each representing ten percent of the overall interaction energy. The dispersion interaction could be dissected into two portions. One third could be related to the dispersion interaction within an ion-pair enhancing the H-bond strength, two thirds stem from dispersion interaction between the ion-pairs. This distribution of dispersion interaction is reflected in the far infrared (FIR) spectra. The H-bond band is shifted weaker than the low frequency band where the latter indicates diffuse cation–anion interaction and H-bond bending motions. Finally, we can dissect the different types of interaction energies indicating their characteristic influence on vibrational modes in the FIR.
- ItemA simple guiding principle for the temperature dependence of the solubility of light gases in imidazolium-based ionic liquids derived from molecular simulations(Cambridge : RSC Publ., 2016) Kerlé, Daniela; Namayandeh Jorabchi, Majid; Ludwig, Ralf; Wohlrab, Sebastian; Paschek, DietmarWe have determined the temperature dependence of the solvation behavior of a large collection of important light gases in imidazolium-based ionic liquids with the help of extensive molecular dynamics simulations. The motivation of our study is to unravel common features of the temperature dependent solvation under well controlled conditions, and to provide a guidance for cases, where experimental data from different sources disagree significantly. The solubility of molecular hydrogen, oxygen, nitrogen, methane, krypton, argon, neon and carbon dioxide in the imidazolium based ionic liquids of type 1-n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][NTf2]) with varying alkyl side chain lengths n = 2, 4, 6, 8 is computed for a temperature range between 300 K and 500 K at 1 bar. By applying Widom's particle insertion technique and Bennet's overlapping distribution method, we are able to determine the temperature dependent solvation free energies of those selected light gases in simulated imidazolium based ionic liquids with high statistical accuracy. Our simulations demonstrate that the magnitude of the solvation free energy of a gas molecule at a chosen reference temperature and that of its temperature-derivatives are intimately related to one another. We conclude that this "universal" behavior is rooted in a solvation entropy-enthalpy compensation effect, which seems to be a defining feature of the solvation of small molecules in ionic liquids. The observations lead to simple analytical relations, determining the temperature dependence of the solubility data based on the absolute solubility at a certain reference temperature. By comparing our results with available experimental data from many sources, we can show that our approach is particularly helpful for providing reliable estimates for the solvation behavior of very light gases, such as hydrogen, where conflicting experimental data exist.
- ItemSpectroscopic evidence of 'jumping and pecking' of cholinium and H-bond enhanced cation-cation interaction in ionic liquids(Cambridge : RSC Publ., 2015) Knorr, Anne; Fumino, Koichi; Bonsa, Anne-Marie; Ludwig, RalfThe subtle energy-balance between Coulomb-interaction, hydrogen bonding and dispersion forces governs the unique properties of ionic liquids. To measure weak interactions is still a challenge. This is in particular true in the condensed phase wherein a melange of different strong and directional types of interactions is present and cannot be detected separately. For the ionic liquids (2-hydroxyethyl)-trimethylammonium (cholinium) bis(trifluoro-methylsulfonyl)amide and N,N,N-trimethyl-N-propylammonium bis(trifluoromethylsulfonyl)amide which differ only in the 2-hydroxyethyl and the propyl groups of the cations, we could directly observe distinct vibrational signatures of hydrogen bonding between the cation and the anion indicated by ‘jumping and pecking’ motions of cholinium. The assignment could be confirmed by isotopic substitution H/D at the hydroxyl group of cholinium. For the first time we could also find direct spectroscopic evidence for H-bonding between like-charged ions. The repulsive Coulomb interaction between the cations is overcome by cooperative hydrogen bonding between the 2-hydroxyethyl functional groups of cholinium. This H-bond network is reflected in the properties of protic ionic liquids (PILs) such as viscosities and conductivities.
- ItemLike-likes-Like: Cooperative Hydrogen Bonding Overcomes Coulomb Repulsion in Cationic Clusters with Net Charges up to Q=+6e(Weinheim : Wiley-VCH Verl., 2018-4-26) Niemann, Thomas; Stange, Peter; Strate, Anne; Ludwig, RalfQuantum chemical calculations have been employed to study kinetically stable cationic clusters, wherein the monovalent cations are trapped by hydrogen bonding despite strongly repulsive electrostatic forces. We calculated linear and cyclic clusters of the hydroxy-functionalized cation N-(3-hydroxypropyl) pyridinium, commonly used as cation in ionic liquids. The largest kinetically stable cluster was a cyclic hexamer that very much resembles the structural motifs of molecular clusters, as known for water and alcohols. Surprisingly, strong cooperative hydrogen bonds overcome electrostatic repulsion and result in cationic clusters with a high net charge up to Q=+6e. The structural, spectroscopic, and electronic signatures of the cationic and related molecular clusters of 3-phenyl-1-propanol could be correlated to NBO parameters, supporting the existence of “anti-electrostatic” hydrogen bonds (AEHB), as recently suggested by Weinhold. We also showed that dispersion forces enhance the cationic cluster formation and compensate the electrostatic repulsion of one additional positive charge.
- ItemDeuteron quadrupole coupling constants and reorientational correlation times in protic ionic liquids(Cambridge : RSC Publ., 2016) Strauch, Matthias; Bonsa, Anne-Marie; Golub, Benjamin; Overbeck, Viviane; Michalik, Dirk; Paschek, Dietmar; Ludwig, RalfWe describe a method for the accurate determination of deuteron quadrupole coupling constants χD for N–D bonds in triethylammonium-based protic ionic liquids (PILs). This approach was first introduced by Wendt and Farrar for O–D bonds in molecular liquids, and is based on the linear relationship between the deuteron quadrupole coupling constants χD, and the proton chemical shifts δ1H, as obtained from DFT calculated properties in differently sized clusters of the compounds. Thus the measurement of δ1H provides an accurate estimate for χD, which can then be used for deriving reorientational correlation-times τND, by means of NMR deuteron quadrupole relaxation time measurements. The method is applied to pure PILs including differently strong interacting anions. The obtained χD values vary between 152 and 204 kHz, depending on the cation–anion interaction strength, intensified by H-bonding. We find that considering dispersion corrections in the DFT-calculations leads to only slightly decreasing χD values. The determined reorientational correlation times indicate that the extreme narrowing condition is fulfilled for these PILs. The τc values along with the measured viscosities provide an estimate for the volume/size of the clusters present in solution. In addition, the correlation times τc, and the H-bonded aggregates were also characterized by molecular dynamics (MD) simulations.