Reaction Mechanism of Pd-catalyzed "CO-free" Carbonylation Reaction Uncovered by In-situ Spectroscopy: The Formyl Mechanism

Robert Geitner; Andrei Gurinov; Tianbai Huang; Stefan Kupfer; Stefanie Graefe; Bert Weckhuysen

doi:10.1002/anie.202011152

Reaction Mechanism of Pd-catalyzed "CO-free" Carbonylation Reaction Uncovered by In-situ Spectroscopy: The Formyl Mechanism

Robert Geitner, Andrei Gurinov, Tianbai Huang, Stefan Kupfer, Stefanie Graefe, Bert Weckhuysen

Friedrich Schiller University Jena: Friedrich-Schiller-Universitat Jena, Institute for Physical Chemistry, GERMANY.

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

"CO-free" carbonylation reactions, where synthesis gas (CO/H2) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received wide spread attention in homogeneous catalysis lately. Although a broad range of organics is available via this method, still relatively little is known about the precise reaction mechanism. In this work, we used in-situ nuclear magnetic resonance (NMR) spectroscopy to unravel the mechanism of the alkoxycarbonylation of alkenes using different surrogate molecules. In contrast to previous hypotheses no carbon monoxide could be found during the reaction. Instead the reaction proceeds via the C-H activation of in-situ generated methyl formate. On the basis of quantitative NMR experiments, a kinetic model involving all major intermediates is built which enables the knowledge-driven optimization of the reaction. Finally, a new reaction mechanism is proposed on the basis of in-situ observed Pd-hydride, Pd-formyl and Pd-acyl species.

Original language	English
Pages (from-to)	3422-3427
Number of pages	6
Journal	Angewandte Chemie-International Edition
Volume	60
Issue number	7
Early online date	4 Nov 2020
DOIs	https://doi.org/10.1002/anie.202011152
Publication status	Published - 15 Feb 2021

Bibliographical note

Funding Information:
R.G. gratefully acknowledges a Research Scholarship from the German Research Foundation under the grant number GE3112/2-1. The authors would like to thank Johan Jastrzebski (Utrecht University) for assistance during the ex situ NMR measurements and the Organic Chemistry and Catalysis group at Utrecht University for NMR measurement time. The authors thank Hugo van Ingen and Marc Baldus for valuable advice on the NMR experiments. A.G. is supported by uNMR-NL, an NWO-funded National Roadmap Large-Scale Facility grant for the Netherlands (grant no. 184.032.207). Matthias Beller is acknowledged for helpful discussion throughout the project.

Funding Information:
R.G. gratefully acknowledges a Research Scholarship from the German Research Foundation under the grant number GE3112/2‐1. The authors would like to thank Johan Jastrzebski (Utrecht University) for assistance during the ex situ NMR measurements and the Organic Chemistry and Catalysis group at Utrecht University for NMR measurement time. The authors thank Hugo van Ingen and Marc Baldus for valuable advice on the NMR experiments. A.G. is supported by uNMR‐NL, an NWO‐funded National Roadmap Large‐Scale Facility grant for the Netherlands (grant no. 184.032.207). Matthias Beller is acknowledged for helpful discussion throughout the project.

Publisher Copyright:
© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Keywords

carbonylation
in situ spectroscopy
kinetics
palladium
reaction mechanisms

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Cite this

@article{28eab91d287c4a2dad1a8c4d82937c4b,

title = "Reaction Mechanism of Pd-catalyzed {"}CO-free{"} Carbonylation Reaction Uncovered by In-situ Spectroscopy: The Formyl Mechanism",

abstract = "{"}CO-free{"} carbonylation reactions, where synthesis gas (CO/H2) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received wide spread attention in homogeneous catalysis lately. Although a broad range of organics is available via this method, still relatively little is known about the precise reaction mechanism. In this work, we used in-situ nuclear magnetic resonance (NMR) spectroscopy to unravel the mechanism of the alkoxycarbonylation of alkenes using different surrogate molecules. In contrast to previous hypotheses no carbon monoxide could be found during the reaction. Instead the reaction proceeds via the C-H activation of in-situ generated methyl formate. On the basis of quantitative NMR experiments, a kinetic model involving all major intermediates is built which enables the knowledge-driven optimization of the reaction. Finally, a new reaction mechanism is proposed on the basis of in-situ observed Pd-hydride, Pd-formyl and Pd-acyl species.",

keywords = "carbonylation, in situ spectroscopy, kinetics, palladium, reaction mechanisms",

author = "Robert Geitner and Andrei Gurinov and Tianbai Huang and Stefan Kupfer and Stefanie Graefe and Bert Weckhuysen",

note = "Funding Information: R.G. gratefully acknowledges a Research Scholarship from the German Research Foundation under the grant number GE3112/2-1. The authors would like to thank Johan Jastrzebski (Utrecht University) for assistance during the ex situ NMR measurements and the Organic Chemistry and Catalysis group at Utrecht University for NMR measurement time. The authors thank Hugo van Ingen and Marc Baldus for valuable advice on the NMR experiments. A.G. is supported by uNMR-NL, an NWO-funded National Roadmap Large-Scale Facility grant for the Netherlands (grant no. 184.032.207). Matthias Beller is acknowledged for helpful discussion throughout the project. Funding Information: R.G. gratefully acknowledges a Research Scholarship from the German Research Foundation under the grant number GE3112/2‐1. The authors would like to thank Johan Jastrzebski (Utrecht University) for assistance during the ex situ NMR measurements and the Organic Chemistry and Catalysis group at Utrecht University for NMR measurement time. The authors thank Hugo van Ingen and Marc Baldus for valuable advice on the NMR experiments. A.G. is supported by uNMR‐NL, an NWO‐funded National Roadmap Large‐Scale Facility grant for the Netherlands (grant no. 184.032.207). Matthias Beller is acknowledged for helpful discussion throughout the project. Publisher Copyright: {\textcopyright} 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",

year = "2021",

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doi = "10.1002/anie.202011152",

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T1 - Reaction Mechanism of Pd-catalyzed "CO-free" Carbonylation Reaction Uncovered by In-situ Spectroscopy

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AU - Geitner, Robert

AU - Gurinov, Andrei

AU - Huang, Tianbai

AU - Kupfer, Stefan

AU - Graefe, Stefanie

AU - Weckhuysen, Bert

N1 - Funding Information: R.G. gratefully acknowledges a Research Scholarship from the German Research Foundation under the grant number GE3112/2-1. The authors would like to thank Johan Jastrzebski (Utrecht University) for assistance during the ex situ NMR measurements and the Organic Chemistry and Catalysis group at Utrecht University for NMR measurement time. The authors thank Hugo van Ingen and Marc Baldus for valuable advice on the NMR experiments. A.G. is supported by uNMR-NL, an NWO-funded National Roadmap Large-Scale Facility grant for the Netherlands (grant no. 184.032.207). Matthias Beller is acknowledged for helpful discussion throughout the project. Funding Information: R.G. gratefully acknowledges a Research Scholarship from the German Research Foundation under the grant number GE3112/2‐1. The authors would like to thank Johan Jastrzebski (Utrecht University) for assistance during the ex situ NMR measurements and the Organic Chemistry and Catalysis group at Utrecht University for NMR measurement time. The authors thank Hugo van Ingen and Marc Baldus for valuable advice on the NMR experiments. A.G. is supported by uNMR‐NL, an NWO‐funded National Roadmap Large‐Scale Facility grant for the Netherlands (grant no. 184.032.207). Matthias Beller is acknowledged for helpful discussion throughout the project. Publisher Copyright: © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

PY - 2021/2/15

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N2 - "CO-free" carbonylation reactions, where synthesis gas (CO/H2) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received wide spread attention in homogeneous catalysis lately. Although a broad range of organics is available via this method, still relatively little is known about the precise reaction mechanism. In this work, we used in-situ nuclear magnetic resonance (NMR) spectroscopy to unravel the mechanism of the alkoxycarbonylation of alkenes using different surrogate molecules. In contrast to previous hypotheses no carbon monoxide could be found during the reaction. Instead the reaction proceeds via the C-H activation of in-situ generated methyl formate. On the basis of quantitative NMR experiments, a kinetic model involving all major intermediates is built which enables the knowledge-driven optimization of the reaction. Finally, a new reaction mechanism is proposed on the basis of in-situ observed Pd-hydride, Pd-formyl and Pd-acyl species.

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