B02 – REMCP Under Confinement and Continuous Flow

Prof. Dr. Michael R. Buchmeiser

University of Stuttgart

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Prof. Dr. Ulrich Tallarek

Philipps University of Marburg

Website

Boshra Atwi

University of Stuttgart

Jan-André Böth

Philipps University of Marburg

Florian Kaltwasser

Philipps University of Marburg

Regio- and Stereoselective Ring-Expansion Metathesis Cyclopolymerization of α,ω-Diynes Under Confinement and Continuous Flow with Multidimensional On-line Reaction Kinetics Analysis

We will perform the so far unprecedented and challenging stereo- and regioselective ring-expansion metathesis cyclopolymerization of diynes to yield cyclic polyenes exclusively based on a single repeat unit with controlled tacticity and molecular weights using tailored catalysts selectively immobilized inside mesoporous silica. We will use steric confinement to selectively tune the regioselectivity of insertion. Control over molecular weight will be achieved by steric confinement. Polymerizations carried out under continuous-flow operation will allow the identification of ring–ring equilibria.

Research focus in the first funding period (2018-2022):
Immobilized Molybdenum Imido, Tungsten Imido- and Tungsten Oxo Alkylidene N-Heterocyclic Carbene Complexes for Olefin Metathesis

Research focus in the second funding period (2018-2022):
Continuous-flow microreactors and multidimensional on-line analytics for catalytic reaction kinetics studies under spatial confinement
Study of Mo-alkylidyne N-heterocyclic carbene (NHC) catalyzed, alkyne metathesis-based macrocyclization and (Z) selective Rh NHC-catalyzed hydrosilylation and hydroamination reactions of alkynes, all under confinement.

Adsorption of Ionic Liquids in Micro-/Mesoporous Silica studied by Small-Angle X-ray Scattering

N. Schnabel, F. Ziegler, M. R. Buchmeiser, T. Sottmann
ChemRxiv 2025.

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Confinement-induced Z-selectivity in the rhodium N-heterocyclic carbene-catalyzed hydroboration of terminal alkynes

B. Atwi, D. Wang, J. R. Bruckner, W. Frey and M. Buchmeiser
Catal. Sci. Technol., 2025, 15, 7059-7066.

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Efficient Ring Closing Metathesis by NHC-Supported(Arylimido)vanadium(V)-Alkylidene Catalysts ContainingPerhalophenoxide Ligands: Exclusive RCM under High SubstrateConcentration

J. Suthala, M. Unoki, M. R. Buchmeiser and K. Nomura
Organometallics 2025, 44, 17, 1870–1875.

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Influence of the supported ionic-liquid layer thickness on Z-selectivity in 1-alkyne hydrosilylation under continuous flow

A. Böth, F. Kaltwasser, Ch. Priedigkeit, B. Atwi, W. Frey, M. R. Buchmeiser and U. Tallarek
Catal. Sci. Technol. 2025, 15, 4012-4023.

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Influence of Ionic Liquid Film Thickness and Flow Rate on Macrocyclization Efficiency and Selectivity in Supported Ionic Liquid-Liquid Phase Catalysis

M. Högler, T. Kobayashi, H. Kraus, B. Atwi, M. R. Buchmeiser, M. Fyta and N. Hansen
Chem. Eur. J. 2025, 31, e202403237.

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Feed injection in liquid chromatography: Reducing the effect of large-volume injections from purely organic diluents in reversed-phase liquid chromatography

A. Böth, D. Foshag, Ch. Schulz, B. Atwi, S. E. Maier, D. P. Estes, M. R. Buchmeiser, T. van de Goor and U. Tallarek
J. Chromatogr. A 2024, 1730, 465165.

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Asymmetric Rh Diene Catalysis under Confinement: Isoxazole Ring-Contraction in Mesoporous Solids

M. Marshall, Z. Dilruba, A.-K. Beurer, K. Bieck, S. Emmerling, F. Markus, Ch. Vogler, F. Ziegler, M. Fuhrer, S. S. Y. Liu, S. R.Kousik, W. Frey, Y. Traa, J. R. Bruckner, B. Plietker, M. R. Buchmeiser, S. Ludwigs, S. Naumann, P. Atanasova, B. V. Lotsch, A. Zens and S. Laschat
Eur. J. Org. Chem. 2024, 27, e202400283.

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Synthetic and Structural Peculiarities of Neutral and Cationic Molybdenum Imido and Tungsten Oxo Alkylidene Complexes Bearing Weakly Coordinating N-Heterocyclic Carbenes

M.R. Buchmeiser, D. Wang, R. Schowner, L. Stöhr, F. Ziegler, S. Sen and W. Frey
Eur. J. Inorg. Chem. 2024, 27, e202400082.

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Mesoionic N-Heterocyclic Olefins as Initiators for the Lewis Pair Polymerization of Epoxides

I. Haug, J. Reitz, C. Ziane, M. R. Buchmeiser, M. M. Hansmann and S. Naumann
Macromol. Rapid Commun. 2024, 2300716.

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Olefin Metathesis and Stereoselective Ring-Opening Metathesis Polymerization with Neutral and Cationic Molybdenum(VI) Imido and Tungsten(VI) Oxo Alkylidene Complexes Containing N‑Chelating N‑Heterocyclic Carbenes

S. Bhattacharya, F. Ziegler, D. Wang, W. Frey and M. R. Buchmeiser
Organometallics 2024, 43, 6, 677−688.

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Manipulate – techniques to manipulate the surroundings of a synthetic catalyst to control activity and selectivity: general discussion

– GENERAL DISCUSSION – T. Beweries, M. R. Buchmeiser, N. R. Champness, M. Costas, A. Duhme-Klair, J. Echeverría, O. Eisenstein, C. T. J. Ferguson, J. C. Goodall, R. Gramage-Doria, M. Gyton, R. Ham, S. Herres-Pawlis, Ch. L. Johnson, P. Kennepohl, B. Lewandowski, P. R. Linnebank, S. A. Macgregor, K. T. Mahmudov, E. Meeus, M. Navarro, P. Ntola, T. N. Parac-Vogt, R. N. Perutz, A. Poater, D. C. Powers, S. Pullen, P. R. Raithby, Joost N. H. Reek, T. R. Ward, A. S. Weller and H. Wennemers

Faraday Discuss., 2023, 244, 96-118.

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Make – underpinning concepts of the synthesis of systems where non-covalent interactions are important: general discussion

– GENERAL DISCUSSION – T. Beweries, M. R. Buchmeiser, F. E. Bugden, N. R. Champness, B. Chanbasha, M. Costas, J. Echeverria, O. Eisenstein, C. Ferguson, J. C. Goodall, R. Gramage-Doria, M. Greenhalgh, M. Gyton, R. Ham, P. Kennepohl, B. Lewandowski, W.-Ch. Liu, S. A. Macgregor, K. T. Mahmudov, E. Meeus, J. Morris, P. Ntola, T. N. Parac-Vogt, R. N. Perutz, A. Poater, D. Powers, P. R. Raithby, J. N. H. Reek, I. Riddell, T. R. Ward, A. S. Weller and H. Wennemers

Faraday Discuss., 2023, 244, 434-454.

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Betainic and ionic tungsten (VI) imido alkylidene N-heterocyclic olefin complexes

M. R. Buchmeiser, D. Imbrich, D. Wang and S. Naumann
J. Organomet. Chem. 2023, 991, 122674.

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Olefin Metathesis under Spatial Confinement and Continuous Flow: Investigation of Isomeric Side Reactions with a Grubbs–Hoveyda Type Catalyst

A. Böth, T. Roider, F. Ziegler, X. Xie, M. R. Buchmeiser and U. Tallarek
ChemCatChem 2023, 15, e202201268.

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Stereoselective Ring-Opening Metathesis Polymerization
with Tungsten Sulfido Alkylidene N-Heterocyclic Carbene
Complexes

M. R. Buchmeiser, P. Probst, D. Wang, and P. M. Hauser
Macromol. Chem. Phys. 2023, 224, 2200350.

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Effect of liquid confinement on regioselectivity in the hydrosilylation of alkynes with cationic Rh(i) N-heterocyclic carbene catalysts

Panyam P. K. R. and M. R. Buchmeiser
Faraday Discuss., 2023, 244, 39-50.

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Hydrosilylation of Alkynes Under Continuous Flow Using Polyurethane-Based Monolithic Supports with Tailored Mesoporosity

H. Acikalin, P. K. R. Panyam, A. W. Shaikh, D. Wang, S. R. Kousik, P. Atanasova and M. R. Buchmeiser
Macromol. Chem. Phys. 2023, 224, 2200234.

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Molybdenum Alkylidyne Silyloxy N-Heterocyclic Carbene
Complexes – Highly Active Alkyne Metathesis Catalysts that
can be Handled in Air

J. V. Musso, V. Gramm, S. Stein, W. Frey and M. R. Buchmeiser
Eur. J. Inorg. Chem. 2023, 26, e202200649.

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Imaging the Permeability and Passivation Susceptibility of SiO₂ Nanosphere-Based Mesoporous Supports for Molecular Heterogeneous Catalysis under Confinement

S. R. Kousik, F. Ziegler, D. Sipp, A. Rodríguez-Camargo, H. Solodenko, W. Gassner, G. Schmitz, B. V. Lotsch, M. R. Buchmeiser, K. Koynov and P. Atanasova
ACS Appl. Nano Mater. 2022, 5, 10, 14733–14745.

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Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes Confined in Mesoporous Silica: Tuning Transition States Towards Z-Selective Ring-Opening Cross-Metathesis

E. L. Goldstein, F. Ziegler, A.-K. Beurer, Y. Traa, J. R. Bruckner, M. R. Buchmeiser
ChemCatChem 2022,14, e202201008.

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Cationic molybdenum oxo alkylidenes stabilized by N-heterocyclic carbenes: from molecular systems to efficient supported metathesis catalysts

J. V. Musso, J. De J. Silva, M. J. Benedikter, J. Groos, W. Frey, Ch. Copéret and M. R. Buchmeiser
Chem. Sci. 2022,13, 8649-8656.

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Isomers of Molybdenum Imido Alkylidene N‑Heterocyclic Carbene Complexes

I.Elser, R. Schowner, L. Stöhr, K. Herz, M. J. Benedikter, S. Sen, W. Frey, D. Wang, and M. R. Buchmeiser
Organometallics 2022, 41, 10, 1232–1248.

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Olefin-Surface Interactions: A Key Activity Parameter in Silica- Supported Olefin Metathesis Catalysts

Z. J. Berkson, M. Bernhardt, S. Schlapansky, M. J. Benedikter, M. R. Buchmeiser, G. Price, G. J. Sunley and C. Copéret
JACS Au 2022, 2, 3, 777–786.

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Olefin Metathesis in Confinement: Towards Covalent Organic Framework Scaffolds for Increased Macrocyclization Selectivity

S. T. Emmerling, F. Ziegler, F. R. Fischer, R. Schoch, M. Bauer, B. Plietker, M. R. Buchmeiser and B. V. Lotsch
Chem. Eur. J. 2022, 28, e202104108.

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Predicting Catalytic Activity from ¹³C_CH Alkylidene Chemical Shift in Cationic Tungsten Oxo Alkylidene N-Heterocyclic Carbene Complexes

J. V. Musso, R. Schowner, L. Falivene, W. Frey, L. Cavallo and M. R. Buchmeiser
ChemCatChem 2021, 13, 1–15.

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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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Cationic Tungsten Imido Alkylidene N-Heterocyclic Carbene Complexes That Contain Bulky Ligands

R. Schowner, J. V. Musso, W. Frey, and M. R. Buchmeiser
Organometallics 2021, 40, 3145–3157.

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Cationic tungsten imido alkylidene N-heterocyclic carbene complexes for stereospecific ring-opening metathesis polymerization of norbornene derivatives†

J. V. Musso, M. Benedikter, P. Gebel, V. Gramm, D. Wang, R. Schowner and M. R. Buchmeiser
Polym. Chem., 2021, 12, 5979–5985.

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Confinement Effects for Efficient Macrocyclization Reactions with Supported Cationic Molybdenum Imido Alkylidene N‑Heterocyclic Carbene Complexes

F. Ziegler, H. Kraus, M. J. Benedikter, D. Wang, J. R. Bruckner, M. Nowakowski, K. Weißer, H. Solodenko, G. Schmitz, M. Bauer, N. Hansen and M. R. Buchmeiser
ACS Catal. 2021, 11, 11570-11578.

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Highly Reactive Cationic Molybdenum Alkylidyne N-Heterocyclic Carbene Catalysts for Alkyne Metathesis

J. Groos, P. M. Hauser, M. Koy, W. Frey and M. R. Buchmeiser

Organometallics 2021, 40, 8, 1178–1184.

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Cationic Tungsten Oxo Alkylidene N‑Heterocyclic Carbene Complexes via Hydrolysis of Cationic Alkylidyne Progenitors

P. M. Hauser, J. V. Musso, W. Frey and M. R. Buchmeiser
Organometallics 2021, 40, 927–937.

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Olefin Ring‐closing Metathesis under Spatial Confinement and Continuous Flow

F. Ziegler, T. Roider, M. Pyschik, Ch. P. Haas, D. Wang, U. Tallarek and M. R. Buchmeiser
ChemCatChem 2021, 13, 1–9.

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Tuning the Latent Behavior of Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization

M. Momin, J. V. Musso, W. Frey and M. R. Buchmeiser
Organometallics 2021, 40, 253-265.

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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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Cationic Group VI Metal Imido Alkylidene N-Heterocyclic Carbene Nitrile Complexes: Bench-Stable, Functional Group Tolerant Olefin Metathesis Catalysts

M. J. Benedikter, J. V. Musso, W. Frey, R. Schowner and M. R. Buchmeiser
Angew. Chem. Int. Ed. 2021, 60, 1374-1382.

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Olefin Ring‐closing Metathesis under Spatial Confinement: Morphology−Transport Relationships

U. Tallarek, J. Hochstrasser, F. Ziegler, X. Huang, Ch. Kübel and M. R. Buchmeiser
ChemCatChem 2021, 13, 281-292.

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Synthesis of Tungsten(VI) Imido Alkylidene Bispyrrolide Complexes via the Isocyanate Route

J. V. Musso, M. J. Benedikter, P. Gebel, I. Elser, W. Frey and M. R. Buchmeiser
Organometallics 2020, 39, 3072–3076.

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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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Group 6 metal alkylidene and alkylidyne N-heterocyclic carbene complexes for olefin and alkyne metathesis

– REVIEW – M. J. Benedikter, F. Ziegler, J. Groos, P. M. Hauser, R. Schowner and M. R. Buchmeiser
Coord. Chem. Rev. 2020, 415, 213315.

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Cationic Tungsten Alkylidyne N‑Heterocyclic Carbene Complexes: Synthesis and Reactivity in Alkyne Metathesis

P. M. Hauser, M. van der Ende, J. Groos, W. Frey, D. Wang and M. R. Buchmeiser
Eur. J. Inorg. Chem. 2020, 3070-3082.

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Reversible N‐ Heterocyclic Carbene‐Induced α‐H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes

J. V. Musso, M. J. Benedikter, D. Wang, W. Frey, H. J. Altmann and M. R. Buchmeiser
Chem. Eur. J. 2020, 26, 8709-8713.

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Stereoselective Olefin Ring-Opening Cross Metathesis Catalyzed by Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes

M. Momin, G. M. Nagy and M. R. Buchmeiser
Adv. Synth. Catal. 2019, 361, 5596-5604.

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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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Regio- and Stereospecific Cyclopolymerization of α,ω-Diynes by Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes

P. Probst, I. Elser, R. Schowner, M. J. Benedikter and M. R. Buchmeiser
Macromol. Rapid Commun. 2020, 41, 1900398.

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Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes Containing Pyrrolide Ligands: Access to Catalysts with Sterically Demanding Alkoxides

I. Elser, M. J. Benedikter, R. Schowner, W. Frey, D. Wang and M. R. Buchmeiser
Organometallics 2019, 38, 2461-2471.

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Synthesis of trans-Isotactic Poly(norbornene)s through Living Ring-Opening Metathesis Polymerization Initiated by Group VI Imido Alkylidene N-Heterocyclic Carbene Complexes

M. J. Benedikter, R. Schowner, I. Elser, P. Werner, K. Herz, L. Stöhr, D. A. Imbrich, G. M. Nagy, D. Wang and M. R. Buchmeiser
Macromolecules 2019, 52, 4059-4066.

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