C04 – Simulations of Chemical Reactivities

Prof. Dr. Johannes Kästner

University of Stuttgart

Website

Severin Haid

University of Stuttgart

Alexander Beck

University of Stuttgart

Lisa Schmoltzi

University of Stuttgart

Simulation of chemical reactivities

We will utilize quantum-chemical methods to obtain free-energy profiles of catalytic reaction mechanisms. Rate constants derived from these profiles enable microkinetic modeling, which is validated against experimental concentration-time data. Fitting provides “experimental barriers” for comparison with computed ones, resolving missing pathways or wrong barriers. We will also compute NMR and vibrational spectra to aid in the assignment. The simulations give molecular insight for the rational use of confinement effects.

Research focus in the second funding period (2022-2026):
Simulation of chemical reactivities, QM/MM, DFT: Simulation of reaction mechanisms, barriers, turnover frequencies, selectivities, and steric requirements for the new reactions entering the CRC.

Research Questions

What are the atomistic details of the reaction mechanisms of olefin metathesis, rhodium-catalyzed asymmetric addition reactions, or ruthenium-catalyzed amine formation? Our understanding of the reaction mechanism allows us to tailor the properties of linkers and pores to the reaction.
Which ingredients are needed to create large-pore COFs? Interlayer displacements of 2D COFs reduce their pore size. Substitutions anchor each layer to the next one. Our simulations shed light on the energetics of structural rearrangements.
How do molecules fragment and desorb in atom-probe tomography? Computational techniques needed to be established to help the extension of APT to soft matter.

Mesoporous Confinement Enables Activity Boost in Cooperative Asymmetric Catalysis in Analogy to Enzymes

L. Rautenbach, M. Nandeshwar, E. Goldstein, M. Högler, M. Häußler, A. Allgaier, A. Bauer, D. Hornung, A. Beck, C. Franke, J. Osterbrink, J. R. Bruckner, J. Kästner, J. van Slageren, J. Pleiss, N. Hansen, M. R. Buchmeiser and R. Peters
ACS Catal 2026, 16, 11, 10371–10384.

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Tuning Regioselectivity in Cyclopolymerization through Carbene Ligand Size Modulation in Molybdenum Imido Alkylidene Catalysts

K. Kundu, S. Haid, P. Probst, L. Stöhr, P. Hauser, W. Frey, J. Kästner and M. R. Buchmeiser
Macromolecules 2026, 59, 3, 1262–1272.

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Chiral Rh diene NHC Complexes and their Application in Rh-Catalyzed Cycloisomerization of Enynes

D. Batman, M. Kirchhof, S. Haid, K. Gugeler, A. Beck, W. Frey, J. Osterbrink, B. Sarkar, A. Zens, J. Kästner, S. Laschat
ChemRxiv 2026.

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Correlating the Reactivity of Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes in Ene-Yne Metathesis and Cyclopolymerization

S. Mohanty, S. Haid, J. Kästner and M. R. Buchmeiser
Organometallics 2026, 45,1, 27–35.

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Class-II-aldolase-mimicking polyfunctional Lewis acid/azolium–aryloxide catalysts in direct enantioselective nitro-aldol additions

K. Jangid, L. A. Schmoltzi, A. Allgaier, R. Kataria, D. M. Wanner, J. Herrmann, J. Gschwind, S. Münch, J. van Slageren, J. Kästner and R. Peters
Org. Chem. Front. 2026,13, 1014-1028.

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Tunable Endo/Exo Selectivity in Direct Catalytic Asymmetric 1,3-Dipolar Cycloadditions with Polyfunctional Lewis Acid / Azolium–Aryloxide Catalysts

A. Bürstner, P. M. Becker, A. Allgaier, L. Pfitzer, D. M. Wanner, J. Dollinger, F. Willig, J. Herrmann, V. Miskov-Pajic, A. C. Hans, W. Frey, J. van Slageren, J. Kästner and R. Peters
Angew. Chem. Int. Ed. 2025, 64, e202508024.

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Linker-Cluster Cooperativity in Confinement of Proline-Functionalized Zr-Based Metal-Organic Frameworks and its Effect on the Organocatalytic Aldol Reaction

Z. Dilruba, A. Dadgar Yeganeh, S. Kolin, S. Noor, H. Shatla, C. Wieland, B.-H. Yu, K. Gugeler, A. Zens, J. Kästner, D. Estes, K. Pluhackova, S. Krause, S. Laschat
Inorg. Chem. Front., 2025, Advance Article

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Computational Approach for Determining Molecular Diameters and Access to Pores

K. Gugeler, J. Kästner and M. Dyballa
ACS Catal. 2025, 15, 6, 4798–4816.

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Origin of Stereoselectivity in Ring Opening Metathesis Polymerization with Cationic Molybdenum Imido Alkylidene CAAC Complexes

K. Kundu, S. Haid, M. R. Schäfer, W. Frey, J. Kästner and M. R. Buchmeiser
ACS Catal. 2025, 15, 738−747.

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Structural Characterization of Surface Immobilized Platinum Hydrides by Sensitivity-Enhanced ¹⁹⁵Pt Solid State NMR Spectroscopy and DFT Calculations

Structural Characterization of Surface Immobilized Platinum Hydrides by Sensitivity-Enhanced 195Pt Solid State NMR Spectroscopy and DFT Calculations

B. A. Atterberry, E. Wimmer, S. Klostermann, W. Frey, J. Kästner, D. Estes and A. J Rossini
Chem. Sci., 2025, 16, 1271-1287.

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Probing Self-Diffusion of Guest Molecules in a Covalent Organic Framework: Simulation and Experiment

L. Grunenberg, Ch. Keßler, T. Wei Teh, R. Schuldt, F. Heck, J. Kästner, J. Groß, N. Hansen and B. V. Lotsch
ACS Nano 2024, 18, 25, 16091–16100.

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Stereoselective Ring Expansion Metathesis Polymerization with Cationic Molybdenum Alkylidyne N-Heterocyclic Carbene Complexes

P. Probst, J. Groos, D. Wang, A. Beck, K. Gugeler, J. Kästner, W. Frey and M. R. Buchmeiser
J. Am. Chem. Soc. 2024, 146, 12, 8435–8446.

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Modulation of peripheral functional groups for the enhancement of electrochemical HER activity in bimetallic Ni-containing triply-fused porphyrins

A. S. Hazari, S. Chandra, P. M. Becker, H. Liu, E. Klemm, J. Kästner, B. Sarkar
ChemRxiv 2024.

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Chirality Transfer of Stereogenic Boron Centers Enabled by a S_N2-Type Mechanism

Y. Stöckl, K. Gugeler, C. M. Holzwarth, W. Frey, S. Wegner, B. Claasen, A. Zens, D. Gudat, Ch. P. Sindlinger, J. Kästner and S. Laschat
Organometallics 2024, 43, 3, 330–340.

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Performance of two complementary machine-learned potentials in modelling chemically complex systems

K. Gubaev, V. Zaverkin, P. Srinivasan, A. I. Duff, J. Kästner and B. Grabowski
npj Comput Mater 2023, 9, 129.

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Neutral and Cationic Molybdenum Imido Alkylidene Cyclic Alkyl Amino Carbene (CAAC) Complexes for Olefin Metathesis

K. Kundu, J. V. Musso, M. J. Benedikter, W. Frey, K. Gugeler, J. Kästner and M. R. Buchmeiser
Chem. Eur. J. 2023, 29, e202301818.

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Cooperative Lewis Acid–1,2,3-Triazolium–Aryloxide Catalysis: Pyrazolone Addition to Nitroolefins as Entry to Diaminoamides

D. M. Wanner, P. M. Becker, S. Suhr, N. Wannenmacher, S. Ziegler, J. Herrmann, F. Willig, J. Gabler, K. Jangid, J. Schmid, A. C. Hans, W. Frey, B. Sarkar, J. Kästner and R. Peters
Angew. Chem. Int. Ed. 2023, 62, e202307317.

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Tethering chiral Rh diene complexes inside mesoporous solids: experimental and theoretical study of substituent, pore and linker effects on asymmetric catalysis

M. Kirchhof, K. Gugeler, A.-K. Beurer, F. R. Fischer, D. Batman, S. M. Bauch, S. Kolin, E. Nicholas, R. Schoch, Ch. Vogler, S. R. Kousik, A. Zens, B. Plietker, P. Atanasova, S. Naumann, M. Bauer, J. R. Bruckner, Y. Traa, J. Kästner and Sabine Laschat
Catal. Sci. Technol., 2023, 13, 3709-3724.

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How Solid Surfaces Control Stability and Interactions of Supported Cationic CuI(dppf) Complexes─A Solid-State NMR Study

M. Schnierle, S. Klostermann, E. Kaya, Z. Li, D. Dittmann, C. Rieg, D. P. Estes, J. Kästner, M. R. Ringenberg and M. Dyballa
Inorg. Chem. 2023, 62, 19, 7283–7295.

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A Practical and Robust Zwitterionic Cooperative Lewis Acid/Acetate/Benzimidazolium Catalyst for Direct 1,4-Additions

A. C. Hans, P. M. Becker, J. Haußmann, S. Suhr, D. M. Wanner, V. Lederer, F. Willig, W. Frey, B. Sarkar, J. Kästner and R. Peters
Angew. Chem. Int. Ed. 2023, 62, e202217519.

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Determination of accessibility and spatial distribution of chiral Rh diene complexes immobilized on SBA-15 via phosphine-based solid-state NMR probe molecules

C. Rieg, M. Kirchhof, K. Gugeler, A. Beurer, L. Stein, K. Dirnberger, W. Frey, J. Bruckner, Y. Traa, J. Kästner, S. Ludwigs, S. Laschat and M. Dyballa
Catal. Sci. Technol., 2023,13, 410-425.

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Influence of layer slipping on adsorption of light gases in covalent organic frameworks: A combined experimental and computational study

C. Kessler, R. Schuldt, S. Emmerling, B. Lotsch, J. Kästner, J. Groß and N. Hansen
Microporous Mesoporous Mater. 2022, 336, 111796.

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Asymmetric Hydroboration of Ketones by Cooperative Lewis Acid–Onium Salt Catalysis: A Quantum Chemical and Microkinetic Study to Combine Theory and Experiment

J. Heitkämper, J. Herrmann, M. Titze, S. M. Bauch, R. Peters and J. Kästner
ACS Catal. 2022, 12, 2, 1497–1507.

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Tungsten Sulfido Alkylidene and Cationic Tungsten Sulfido Alkylidene N-Heterocyclic Carbene Complexes

P. M. Hauser, K. Gugeler, W. Frey, J. Kästner and M. R. Buchmeiser
Organometallics 2021, 40, 23, 4026–4034.

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Interplay of Polarity and Confinement in Asymmetric Catalysis with Chiral Rh Diene Complexes in Microemulsions

M. Kirchhof, K. Abitaev, A. Abouhaileh, K. Gugeler, W. Frey, A. Zens, J. Kästner, T. Sottmann and S. Laschat
Chem. Eur. J. 2021, 27, 16853–16870.

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Interlayer Interactions as Design Tool for Large-Pore COFs

S. T. Emmerling, R. Schuldt, S. Bette, L. Yao, R. E. Dinnebier, J. Kästner, and B. V. Lotsch
J. Am. Chem. Soc. 2021, 143, 15711–15722.

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Quantitative Distinction between Noble Metals Located in Mesopores from Those on the External Surface

C. Rieg, D. Dittmann, Z. Li, R. Lawitzki, K. Gugeler, S. Maier, G. Schmitz, J. Kästner, D. P. Estes and M. Dyballa
Chem. Eur. J. 2021, 27, 17012-17023.

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3D Sub-Nanometer Analysis of Glucose in an Aqueous Solution by Cryo-Atom Probe Tomography

T. M. Schwarz, C. Dietrich, J. Ott, E. M. Weikum, R. Lawitzki, H. Solodenko, E. Hadjixenophontos, B. Gault, J. Kästner, G. Schmitz and P. Stender
Sci. Rep. 2021, 11, 11607.

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Charge Distribution in Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: A Combined X-ray, XAS, XES, DFT, Mössbauer, and Catalysis Approach

M. J. Benedikter, J. V. Musso, M. K. Kesharwani, K. L. Sterz, I. Elser, F. Ziegler, F. Fischer, B. Plietker, W. Frey, J. Kästner, M. Winkler, J. van Slageren, M. Nowakowski, M. Bauer and M. R. Buchmeiser
ACS Catal. 2020, 10, 14810–14823.

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Ruthenium‐Catalyzed Secondary Amine Formation Studied by Density Functional Theory

L. Hückmann, S. Álvarez‐Barcia, M. Fuhrer, B. Plietker and J. Kästner
ChemCatChem 2021, 13, 1383 –1388.

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Field evaporation and atom probe tomography of pure water tips

T. M. Schwarz, E. M. Weikum, K. Meng, E. Hadjixenophontos, C. A. Dietrich, J. Kästner, P. Stender and G. Schmitz
Sci. Rep. 2020, 10, 20271.

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Evaporation and Fragmentation of Organic Molecules in Strong Electric Fields Simulated with DFT

C. A. Dietrich, R. Schuldt, D. Born, H. Solodenko, G. Schmitz and J. Kästner
J. Phys. Chem. A 2020, 124, 8633–8642.

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Experimental and Theoretical Study on the Role of Monomeric vs Dimeric Rhodium Oxazolidinone Norbornadiene Complexes in Catalytic Asymmetric 1,2- and 1,4-Additions

M. Kirchhof, K. Gugeler, F. R. Fischer, M. Nowakowski, A. Bauer, S. Alvarez-Barcia, K. Abitaev, M. Schnierle, Y. Qawasmi, W. Frey, A. Baro, D. P. Estes, T. Sottmann, M. R. Ringenberg, B. Plietker, M. Bauer, J. Kästner and S. Laschat
Organometallics 2020, 39, 3131–3145.

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Reaction Mechanism of Ring-Closing Metathesis with a Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Catalyst

M. K. Kesharwani, I. Elser, J. V. Musso, M. R. Buchmeiser and J. Kästner

Organometallics 2020, 39, 3146–3159.

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Molybdenum and Tungsten Alkylidyne Complexes Containing Mono- and Bidentate N-Heterocyclic Carbenes

I. Elser, J. Groos, P. M. Hauser, M. Koy, M. van der Ende, D. Wang, W. Frey, K. Wurst, J. Meisner, J. Kästner and M. R. Buchmeiser
Organometallics 2019, 38, 4133−4146.

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Proton Affinities of N-Heterocyclic Olefins and Their Implications for Organocatalyst Design

R. Schuldt, J. Kästner and S. Naumann
J. Org. Chem. 2019, 84, 2209–2218.

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C04 – Simulations of Chemical Reactivities

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