Sub-Coordinators: Prof. Dr. Gabriele Sadowski     Hon.-Prof. Dr. Matthias Stein
Researcher: M. Sc. Froze Jameel

Solvents do have an influence on chemical reaction equilibria (and thus the yield) and the kinetics of a chemical reaction. In multiphase systems, the different solubilities of reactants and products will also have an effect on these.

We are using recent results from homogenous catalysis to selectively control and drive complex chemical reactions in solution by steering the thermodynamics (chemical equilibria) and kinetics (from transition state theory). By combining the results of an ideal quantum chemical model system and a realistic non-ideal system in terms of activity coefficients, such a control will become feasible. Finally, a suitable reaction media will be suggested to obtain the desired products.

Connected projects within Collaborative Research Centre/Transregio 63

A3 (Hamel, Seidel-Morgenstern): Kinetics of reductive amination and hydroamination in reactive multiphase fluid systems

A9 (Sadowski, Enders): Solubilization of weakly polar compounds in micellar systems

A11 (Seidensticker, Vogt): Homogeneously catalyzed reductive amination of long-chain aldehydes and hydroaminomethylation of long-chain alkenes with integrated separation in thermo-regulated solvent systems

B1 (Sundmacher, Zähringer): Exchange of kinetic data and models, validation of the optimal solvent system as well as dosing and temperature trajectories on reactor and process level

B9 (Kienle, Sundmacher): Experimental validation of optimal solvent systems, optimal reactor design and operation for liquid multiphase systems

D1 (Engell, Sadowski, Sundmacher): Providing of simplified and mechanistic kinetic models for process development, optimization and evaluation of kinetics in a pilot scale plant, general rules for the evaluation of tandem reactions (multi-pot vs. single-pot synthesis)

Recent Publications

Huxoll, F.; Kampwerth, A.; Seidensticker, T.; Vogt, D.; Sadowski, G. Predicting Solvent Effects on Homogeneity and Kinetics of the Hydroaminomethylation: A Thermodynamic Approach Using PC-SAFT. Industrial & Engineering Chemistry Research, 61 (5), 2323-2332, 2022. [DOI: 10.1021/acs.iecr.1c03891]

Jameel, F.; Stein, M. The many roles of solvent in homogeneous catalysis - The reductive amination showcase. Journal of Catalysis, 405, 24-34, 2022. [DOI:10.1016/j.jcat.2021.11.010]

Boz, E.; Stein M. Accurate Receptor-Ligand Binding Free Energies from Fast QM Conformational Chemical Space Sampling. Int. J. Mol. Sci. 22, 6, 3078, 2021. [DOI:10.3390/ijms22063078]

Huxoll, F.; Jameel, F.; Bianga, J.; Seidensticker, T.; Stein, M.; Sadowski, G.; Vogt, D. Solvent Selection in Homogeneous Catalysis—Optimization of Kinetics and Reaction Performance. ACS Catalysis 11, 2, 590-594, 2021. [DOI: 10.1021/acscatal.0c04431]

Huxoll, F.; Heyng, M.; Andreeva, I. V.; Verevkin, S. P.; Sadowski, G. Thermodynamic Properties of Biogenic Amines and Their Solutions. Journal of Chemical & Engineering Data, 66 (7), 2822-2831,  2021. [DOI: 10.1021/acs.jced.1c00202]

Huxoll, F.; Schlüter, S.; Budde, R.; Skiborowski, M.; Petzold, M.; Böhm, L.; Kraume, M.; Sadowski, G. Phase Equilibria for the Hydroaminomethylation of 1-Decene. Journal of Chemical & Engineering Data, 66 (12), 4484-4495, 2021. [DOI: 10.1021/acs.jced.1c00561]

Jameel, F.; Stein, M. Solvent effects in hydroformylation of long-chain olefins, Molecular Catalysis, 503, 111429, 2021.[DOI:10.1016/j.mcat.2021.111429]

Kirschtowski, S.; Jameel, F.; Stein, M.; Seidel-Morgenstern A.; Hamel, C. Kinetics of the Reductive Amination of 1-Undecanal in Thermomorphic Multicomponent System, Chemical Engineering Science, 230, 116187, 2021. [doi:10.1016/j.ces.2020.116187]

Pandey, I. K.;  Agarwal, T; Stein, M.; Kaur-Ghumaan, S. Switching Site Reactivity in Hydrogenase Model Systems by Introducing a Pendant Amine Ligand. ACS Omega Article, 6, 6, 4192–4203, 2021. [DOI: 10.1021/acsomega.0c04901]

Kuehne, I. A.; Barker, A.; Zhang, F.; Stamenov, P.; O'Doherty, O.; Müller-Bunz, H.; Stein, M.; Rodriguez, B. J.; MORGAN, G. G. Modulation of Jahn-Teller Distortion and Electromechanical Response in a Mn³⁺ Spin Crossover Complex. J. Phys.: Condens. Matter, In Press, 2020. [doi.org/10.1088/1361-648X/ab82d1]

Jameel, F.; Kohls, E.;  Stein, M. Mechanism and Control of the Palladium‐Catalyzed Alkoxycarbonylation of Oleochemicals from Sustainable Sources. ChemCatChem, 11(19), 4894-4906, 2019. [doi.org/10.1002/cctc.201901097]

Boz, E.; Tüzün, N. Ş.; Stein, M. Computational investigation of the control of the thermodynamics and microkinetics of the reductive amination reaction by solvent coordination and a co-catalyst. RSC Adv., 8, 36662-366674, 2018. [doi:10.1039/C8RA08135B]

Lemberg, M.; Schomäcker, R.; Sadowski, G. Thermodynamic prediction of the solvent effect on a transesterification reaction. Chem. Eng., 176, 264-269, 2018. [doi.org/10.1016/j.ces.2017.10.033]

Melnikov, S. M.; Stein, M. Solvation and Dynamics of CO2 in Aqueous Alkanolamine Solutions. ACS Sustainable Chem. Eng. 2018. [DOI: 10.1021/acssuschemeng.8b04666]

Kohls, E.; Stein, M. Vibrational scaling factors for Rh(I) carbonyl compounds in homogeneous catalysis. MASA, 38(1), 43-56, 2017. [doi:10.20903/csnmbs.masa.2017.38.1.100]

Kohls, E.; Stein, M. The thermochemistry of long chain olefin isomers during hydroformylation. New J. Chem., 15, 7347-7355, 2017. [doi: 10.1039/c7nj01396e]

Lemberg, M.; Sadowski, G.; Gerlach, M.; Kohls, E.; Stein, M.; Hamel, C.; Seidel-Morgenstern, A. Predicting solvent effects on the 1-dodecene hydroformylation reaction equilibrium. AIChE J., 63(10), 4576-4585, 2017. [doi: 10.1002/aic.15782]

Lemberg, M.; Sadowski, G. Predicting the solvent effect on esterification kinetics. Chem. Phys. Chem., 15, 1977-1980, 2017. [https://doi.org/10.1002/cphc.201700507]

Jörke, A.; Kohls, E.; Triemer, S.; Seidel-Morgenstern, A.; Hamel, C.; Stein, M. Resolution of Structural Isomers of Complex Reaction Mixtures in Homogeneous Catalysis. Chem. Eng. Process., 102, 229-237, 2016. [doi:10.1016/j.cep.2016.01.001]

Lemberg, M.; Sadowski, G. Phase Equilibria for the Hydroesterification of 10-Undecenoic Acid Methyl Ester. J. Chem. Eng. Data., 61(9), 3317-3325, 2016. [doi:10.1021/acs.jced.6b0036]

Chauhan, G.; Stein, M.; Seidel-Morgenstern, A.; Pant, K. K.; Nigam, K. D. P. The thermodynamics and biodegradability of chelating agents upon metal extraction. Chem. Eng. Sci., 137, 768-785, 2015. [doi:10.1016/j.ces.2015.07.02]

Riechert, O.; Husham, M.; Sadowski, G.; Zeiner, T. Solvent effects on esterification equilibria. AIChE J., 61(9), 3000–3011, 2015. [doi:10.1002/aic.14873]

Dissertations

Vogelpohl, Christina Measuring and modeling high-pressure gas solubility in temperature modulated solvent systems. Technische Universität Dortmund, 2016. [More]

Schäfer, E. Simultaneous calculation of fluid phase equilibria and interfacial properties of aprotic solvent mixtures incorporating experimental studies. Technische Universität Dortmund, 2013.
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