Project B02

Continuous-flow and on-line analytics

Project leader(s)
Team

Prof. Dr. Michael R. Buchmeiser

Prof. Dr. Michael R. Buchmeiser

University of Stuttgart

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Prof. Dr. Ulrich Tallarek

Prof. Dr. Ulrich Tallarek

Philipps University of Marburg

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Boshra Atwi

Boshra Atwi

University of Stuttgart

Jan-André Böth

Jan-André Böth

Philipps University of Marburg

Email

Vincent Gramm

Vincent Gramm

University of Stuttgart

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Summary
Publications

Continuous-flow microreactors and multidimensional on-line analytics for catalytic reaction kinetics studies under spatial confinement

We will study 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. The overarching idea in the use of these entirely different catalytic reactions is to develop a unifying concept for confinement effects in catalytic reactions with both large and small substrates. Reactions will be run in continuous-flow microreactors. An instrumental platform with on-line separation and detection will be established to quantify conversion and selectivity under the respective reaction conditions and to determine reaction kinetics rapidly and reproducibly.

Research focus in the 1^st funding period (2018-2022):
Immobilized Molybdenum Imido, Tungsten Imido- and Tungsten Oxo Alkylidene N-Heterocyclic Carbene Complexes for Olefin Metathesis

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

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

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

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

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

Stereoselective Ring-Opening Metathesis Polymerizationwith Tungsten Sulfido Alkylidene N-Heterocyclic CarbeneComplexes

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

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

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

Molybdenum Alkylidyne Silyloxy N-Heterocyclic CarbeneComplexes – Highly Active Alkyne Metathesis Catalysts thatcan 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

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

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

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

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

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

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

Predicting Catalytic Activity from ¹³CCH 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

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

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†

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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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Mechanism of Olefin Metathesis with Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes

Mechanism of Olefin Metathesis with Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes

K. Herz, M. Podewitz, L. Stöhr, D. Wang, W. Frey, K. R. Liedl, S. Sen and M. R. Buchmeiser J. Am. Chem. Soc. 2019, 141, 8264-8276.

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Understanding Synthetic Peculiarities of Cationic Molybdenum (VI) Imido Alkylidene N-Heterocyclic Carbene Complexes

Understanding Synthetic Peculiarities of Cationic Molybdenum (VI) Imido Alkylidene N-Heterocyclic Carbene Complexes

R. Schowner, W. Frey and M. R. Buchmeiser Eur. J. Inorg. Chem. 2019, 1911-1922.

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Functional Precision Polymers via Stereo- and Regioselective Polymerization Using Group 6 Metal Alkylidene and Group 6 and 8 Metal Alkylidene N-Heterocyclic Carbene Complexes

Functional Precision Polymers via Stereo- and Regioselective Polymerization Using Group 6 Metal Alkylidene and Group 6 and 8 Metal Alkylidene N-Heterocyclic Carbene Complexes

M. R. Buchmeiser Macromol. Rapid Commun. 2019, 40, 1800492.

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Molybdenum Imido, Tungsten Imido and Tungsten Oxo Alkylidene N-Heterocyclic Carbene Olefin Metathesis Catalysts

Molybdenum Imido, Tungsten Imido and Tungsten Oxo Alkylidene N-Heterocyclic Carbene Olefin Metathesis Catalysts

M. R. Buchmeiser Chem. Eur. J. 2018, 24, 14295-14301.

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