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- ItemCobalt-catalysed reductive C-H alkylation of indoles using carboxylic acids and molecular hydrogen(Cambridge : RSC, 2017) Cabrero-Antonino, Jose R.; Adam, Rosa; Junge, Kathrin; Beller, MatthiasThe direct CH-alkylation of indoles using carboxylic acids is presented for the first time. The catalytic system based on the combination of Co(acac)3 and 1,1,1-tris(diphenylphosphinomethyl)-ethane (Triphos, L1), in the presence of Al(OTf)3 as co-catalyst, is able to perform the reductive alkylation of 2-methyl-1H-indole with a wide range of carboxylic acids. The utility of the protocol was further demonstrated through the C3 alkylation of several substituted indole derivatives using acetic, phenylacetic or diphenylacetic acids. In addition, a careful selection of the reaction conditions allowed to perform the selective C3 alkenylation of some indole derivatives. Moreover, the alkenylation of C2 position of 3-methyl-1H-indole was also possible. Control experiments indicate that the aldehyde, in situ formed from the carboxylic acid hydrogenation, plays a central role in the overall process. This new protocol enables the direct functionalization of indoles with readily available and stable carboxylic acids using a non-precious metal based catalyst and hydrogen as reductant.
- ItemNickel-Catalyzed Carbonylative Synthesis of Functionalized Alkyl Iodides(Amsterdam : Elsevier B.V., 2018) Peng, J.-B.; Wu, F.-P.; Xu, C.; Qi, X.; Ying, J.; Wu, X.-F.Chemistry; Catalysis; Organic Synthesis © 2018 The Author(s)Functionalized alkyl iodides are important compounds in organic chemistry and biology. In this communication, we developed an interesting nickel-catalyzed carbonylative synthesis of functionalized alkyl iodides from aryl iodides and ethers. With Mo(CO)6 as the solid CO source, both cyclic and acyclic ethers were activated, which is also a challenging topic in organic synthesis. Functionalized alkyl iodides were prepared in moderate to excellent yields with outstanding functional group tolerance. Besides the high value of the obtained products, all the atoms from the starting materials were incorporated in the final products and the reaction had high atom efficiency as well.
- ItemCobalt-Catalyzed Aqueous Dehydrogenation of Formic Acid(Weinheim : Wiley-VCH, 2019) Zhou, Wei; Wei, Zhihong; Spannenberg, Anke; Jiao, Haijun; Junge, Kathrin; Junge, Henrik; Beller, MatthiasAmong the known liquid organic hydrogen carriers, formic acid attracts increasing interest in the context of safe and reversible storage of hydrogen. Here, the first molecularly defined cobalt pincer complex is disclosed for the dehydrogenation of formic acid in aqueous medium under mild conditions. Crucial for catalytic activity is the use of the specific complex 3. Compared to related ruthenium and manganese complexes 7 and 8, this optimal cobalt complex showed improved performance. DFT computations support an innocent non-classical bifunctional outer-sphere mechanism on the triplet state potential energy surface. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemMicro/Mesoporous Zeolitic Composites: Recent Developments in Synthesis and Catalytic Applications(Basel : MDPI, 2016) Vu, Xuan; Armbruster, Udo; Martin, AndreasMicro/mesoporous zeolitic composites (MZCs) represent an important class of hierarchical zeolitic materials that have attracted increasing attention in recent years. By introducing an additional mesoporous phase interconnected with the microporosity of zeolites, a hierarchical porous system of MZCs is formed which facilitates molecular transport while preserving the intrinsic catalytic properties of zeolites. Thus, these materials offer novel perspectives for catalytic applications. Over the years, numerous synthesis strategies toward the formation of MZCs have been realized and their catalytic applications have been reported. In this review, the three main synthesis routes, namely direct synthesis using zeolite precursors, recrystallization of zeolites, and zeolitization of preformed mesoporous materials are thoroughly discussed, with focus on prior works and the most recent developments along with prominent examples given from the literature. In addition, the significant improvement in the catalytic properties of MZCs in a wide range of industrially relevant reactions is presented through several representative cases. Some perspectives for the future development of MZCs are also given.
- Item(μ3-Hydrido)[μ3-2-(trimethylsilyl) ethylidyne-κ3C1:C1:C1] tetrakis[(η5-cyclopentadienyl)cobalt(II)](Chester : International Union of Crystallography, 2013) Haehnel, M.; Spannenberg, A.; Rosenthal, U.In the title compound, [Co4(C5H5) 4(μ3-CCH2SiMe3)(μ3-H)], the Co atoms form a distorted tetrahedron with the ethylidyne moiety bridging three of the Co atoms as well as the hydrido ligand also bridging three of the Co atoms. The Co-Co bond lengths in the Co4tetrahedron vary from 2.3844 (4) to 2.4608 (4) Å. Each Co atom is additionally η5-bonded to a cyclopentadienyl (Cp) anion.
- ItemStability studies of ionic liquid [EMIm][NTf2] under short-term thermal exposure(London : RSC Publishing, 2016) Neise, Christin; Rautenberg, Christine; Bentrup, Ursula; Beck, Martin; Ahrenberg, Mathias; Schick, Christoph; Keßler, Olaf; Kragl, UdoIonic liquids (ILs) as new media for synthesis and as functional fluids in technical applications are still of high interest. Cooling a steel component from an annealing temperature of nearly 850 °C down to room temperature in a liquid bath is a technically important process. The use of ionic liquids offers advantages avoiding film boiling of the quenching medium. However, such a high immersion temperature exceeds the thermal stability of the IL, for example such as [EMIm][NTf2]. To obtain information about formation of potential toxic decomposition products, potential fragments at varied states of decomposition of [EMIm][NTf2] were studied by various spectroscopic and gravimetric methods. For the first time it was possible to quantify fluorine-containing products via mass spectrometry coupled directly with thermogravimetric (TG) measurements. While chemical and spectroscopic analysis of thermally stressed ILs revealed no hints concerning changes of composition after quenching hot steel for several times, the mass-spectrometer (MS) coupled TG analysis gives information by comparing the decomposition behaviour of fresh and used ILs. A number of fragments were detected in low amounts confirming the proposed decomposition mechanism.
- 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).
- ItemA chemometric study in the area of feasible solution of an acid-base titration of N-methyl-6-oxyquinolone(London : RSC Publishing, 2018) Sawall, Mathias; Schmode, Stella; Schröder, Henning; Ludwig, Ralf; Neymeyr, KlausMultivariate curve resolution methods aim at recovering the underlying chemical components from spectroscopic data on chemical reaction systems. In most cases the spectra and concentration profiles of the pure components cannot be uniquely determined from the given spectral data. Instead continua of possible factors exist. This fact is known as rotational ambiguity. The sets of all possible pure component factors can be represented in the so-called area of feasible solutions (AFS). This paper presents an AFS study of the pure component reconstruction problem for a series of UV/Vis spectra taken from an acid-base titration of N-methyl-6-oxyquinolone. Additional information on the equilibrium concentration profiles for a varying acid concentration is taken from fluorescence measurements. On this basis chemometric duality arguments lead to the construction of a unique final solution.
- Item2,6-Bis[(S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-yl]pyridine(Chester : International Union of Crystallography, 2011) Möller, K.; Junge, K.; Spannenberg, A.; Beller, M.The commercially available title compound, C25H 23N3O2, has been known since 1993 [Nesper et al. (1993). Helv. Chim. Acta, 76, 2239-2249], but has not been structurally characterized until now. In the free ligand, the N atoms of both oxazoline rings point in opposite directions. The phenyl rings make dihedral angles of 30.56 (5) and 84.57 (3)° with the pyridine ring and 72.85 (3)° with each other.
- 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.