Divergent Reactivity of an Isolable Nickelacyclobutane

María L. G. Sansores‐paredes; Storm Voort; Martin Lutz; Marc‐etienne Moret

doi:10.1002/anie.202111389

Divergent Reactivity of an Isolable Nickelacyclobutane

María L. G. Sansores‐paredes, Storm Voort, Martin Lutz, Marc‐etienne Moret

Utrecht University

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

Abstract

Nickelacyclobutanes are mostly invoked as reactive intermediates in the reaction of nickel carbenes and olefins to yield cyclopropanes. Nevertheless, early work suggested that other decomposition routes such as β-hydride elimination and even metathesis could be accessible. Herein, we report the isolation and characterization of a stable pentacoordinated nickelacyclobutane incorporated in a pincer complex. The coordination of different coligands to the nickelacyclobutane determines its selective decomposition along cyclopropanation, metathesis or apparent β-hydride elimination pathways. DFT calculations shed light on the mechanism of these different pathways.

Original language	English
Pages (from-to)	26518-26522
Number of pages	5
Journal	Angewandte Chemie-International Edition
Volume	60
Issue number	51
DOIs	https://doi.org/10.1002/anie.202111389
Publication status	Published - 13 Dec 2021

Bibliographical note

Funding Information:
This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No 715060). The X-ray diffractometer has been financed by the Netherlands Organization for Scientific Research (NWO). The computational work was carried out on the Dutch national e-infrastructure with the support of the SURF Foundation. We thank Dr. Johann Jastrzebski for assistance with NMR analysis. The authors thank Prof. P. Chen, Prof. G. van Koten, Prof. R. J. M. Klein Gebbink and Dr. D. L. J. Broere for insightful discussions.

Funding Information:
This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No 715060). The X‐ray diffractometer has been financed by the Netherlands Organization for Scientific Research (NWO). The computational work was carried out on the Dutch national e‐infrastructure with the support of the SURF Foundation. We thank Dr. Johann Jastrzebski for assistance with NMR analysis. The authors thank Prof. P. Chen, Prof. G. van Koten, Prof. R. J. M. Klein Gebbink and Dr. D. L. J. Broere for insightful discussions.

Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Keywords

cyclopropanation
metallacycles
metathesis
nickel
pincer compounds

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Angewandte Chemie - 2021 - Sansores‐Paredes - Divergent Reactivity of an Isolable NickelacyclobutaneFinal published version, 1.12 MBLicence: CC BY

Cite this

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abstract = "Nickelacyclobutanes are mostly invoked as reactive intermediates in the reaction of nickel carbenes and olefins to yield cyclopropanes. Nevertheless, early work suggested that other decomposition routes such as β-hydride elimination and even metathesis could be accessible. Herein, we report the isolation and characterization of a stable pentacoordinated nickelacyclobutane incorporated in a pincer complex. The coordination of different coligands to the nickelacyclobutane determines its selective decomposition along cyclopropanation, metathesis or apparent β-hydride elimination pathways. DFT calculations shed light on the mechanism of these different pathways.",

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Divergent Reactivity of an Isolable Nickelacyclobutane

Abstract

Bibliographical note

Keywords

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