Synthesis and Reactivity of the [NCCCO]− Cyanoketenate Anion

Tongtong Wang; Zhuangzhuang Guo; Laura E. English; Douglas W. Stephan; Andrew R. Jupp; Maotong Xu

doi:10.1002/ange.202402728

Synthesis and Reactivity of the [NCCCO]⁻ Cyanoketenate Anion

Tongtong Wang, Zhuangzhuang Guo, Laura E. English, Douglas W. Stephan, Andrew R. Jupp^*, Maotong Xu^*

^*Corresponding author for this work

Chemistry

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Abstract

Cyanoketene is a fundamental molecule that is actively being searched for in the interstellar medium. Its deprotonated form (cyanoketenate) is a heterocumulene that is isoelectronic to carbon suboxide whose structure has been the subject of debate. However, the investigation of cyanoketene and its derivatives is hampered by the lack of practical synthetic routes to these compounds. We report the first synthesis of the cyanoketenate anion in [K(18‐crown‐6)][NCCCO] (1) as a stable molecule on a multigram scale in excellent yields (>90 %). The structure of this molecule is probed crystallographically and computationally. We also explore the protonation of 1, and its reaction with triphenylsilylchloride and carbon dioxide. In all cases, anionic dimers are formed. The cyanoketene could be synthesized and crystallographically characterized when stabilized by a N‐heterocyclic carbene. The cyanoketenate is a very useful unsaturated building block containing N, C and O atoms that can now be explored with relative ease and will undoubtedly unlock more interesting reactivity.

Original language	English
Article number	e202402728
Number of pages	7
Journal	Angewandte Chemie (International Edition)
Early online date	14 Mar 2024
DOIs	https://doi.org/10.1002/ange.202402728
Publication status	E-pub ahead of print - 14 Mar 2024

Bibliographical note

Acknowledgments
T.W. is grateful for the financial support from the Shanghai Pujiang Program (23PJ1413400) and the Shanghai Post-doctoral Excellence Program (2022573), and the award of a Honorary Postdoctoral Fellowship at the University of Birmingham. M.X is grateful for the financial support from the National Natural Science Foundation of China (22201215), the Fundamental Research Funds for the Central Universities and the award of Distinguished Overseas Young Talents. A.R.J. would like to thank the Royal Society (URF\R1\201636) for funding, and A.R.J and L.E.E. gratefully acknowledge the EPSRC (EP/W036908/1) for funding. The computations described in this paper were performed using the University of Birmingham's BlueBEAR HPC service, see http://www.birmingham.ac.uk/bear for more details. D.W.S. is grateful to NSERC for continued funding and support.

Keywords

cyanoketene
N-heterocyclic carbene
small-molecule activation
carbon monoxide
cumulenes

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Synthesis and Reactivity of the [NCCCO]⁻ Cyanoketenate Anion
Wang, T., Guo, Z., English, L. E., Stephan, D. W., Jupp, A. R. & Xu, M., 9 Apr 2024, (E-pub ahead of print) In: Angewandte Chemie (International Edition) . 7 p., e202402728.
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Cite this

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title = "Synthesis and Reactivity of the [NCCCO]− Cyanoketenate Anion",

abstract = "Cyanoketene is a fundamental molecule that is actively being searched for in the interstellar medium. Its deprotonated form (cyanoketenate) is a heterocumulene that is isoelectronic to carbon suboxide whose structure has been the subject of debate. However, the investigation of cyanoketene and its derivatives is hampered by the lack of practical synthetic routes to these compounds. We report the first synthesis of the cyanoketenate anion in [K(18‐crown‐6)][NCCCO] (1) as a stable molecule on a multigram scale in excellent yields (>90 %). The structure of this molecule is probed crystallographically and computationally. We also explore the protonation of 1, and its reaction with triphenylsilylchloride and carbon dioxide. In all cases, anionic dimers are formed. The cyanoketene could be synthesized and crystallographically characterized when stabilized by a N‐heterocyclic carbene. The cyanoketenate is a very useful unsaturated building block containing N, C and O atoms that can now be explored with relative ease and will undoubtedly unlock more interesting reactivity.",

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author = "Tongtong Wang and Zhuangzhuang Guo and English, {Laura E.} and Stephan, {Douglas W.} and Jupp, {Andrew R.} and Maotong Xu",

note = "Acknowledgments T.W. is grateful for the financial support from the Shanghai Pujiang Program (23PJ1413400) and the Shanghai Post-doctoral Excellence Program (2022573), and the award of a Honorary Postdoctoral Fellowship at the University of Birmingham. M.X is grateful for the financial support from the National Natural Science Foundation of China (22201215), the Fundamental Research Funds for the Central Universities and the award of Distinguished Overseas Young Talents. A.R.J. would like to thank the Royal Society (URF\R1\201636) for funding, and A.R.J and L.E.E. gratefully acknowledge the EPSRC (EP/W036908/1) for funding. The computations described in this paper were performed using the University of Birmingham's BlueBEAR HPC service, see http://www.birmingham.ac.uk/bear for more details. D.W.S. is grateful to NSERC for continued funding and support.",

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AU - Jupp, Andrew R.

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N1 - Acknowledgments T.W. is grateful for the financial support from the Shanghai Pujiang Program (23PJ1413400) and the Shanghai Post-doctoral Excellence Program (2022573), and the award of a Honorary Postdoctoral Fellowship at the University of Birmingham. M.X is grateful for the financial support from the National Natural Science Foundation of China (22201215), the Fundamental Research Funds for the Central Universities and the award of Distinguished Overseas Young Talents. A.R.J. would like to thank the Royal Society (URF\R1\201636) for funding, and A.R.J and L.E.E. gratefully acknowledge the EPSRC (EP/W036908/1) for funding. The computations described in this paper were performed using the University of Birmingham's BlueBEAR HPC service, see http://www.birmingham.ac.uk/bear for more details. D.W.S. is grateful to NSERC for continued funding and support.

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N2 - Cyanoketene is a fundamental molecule that is actively being searched for in the interstellar medium. Its deprotonated form (cyanoketenate) is a heterocumulene that is isoelectronic to carbon suboxide whose structure has been the subject of debate. However, the investigation of cyanoketene and its derivatives is hampered by the lack of practical synthetic routes to these compounds. We report the first synthesis of the cyanoketenate anion in [K(18‐crown‐6)][NCCCO] (1) as a stable molecule on a multigram scale in excellent yields (>90 %). The structure of this molecule is probed crystallographically and computationally. We also explore the protonation of 1, and its reaction with triphenylsilylchloride and carbon dioxide. In all cases, anionic dimers are formed. The cyanoketene could be synthesized and crystallographically characterized when stabilized by a N‐heterocyclic carbene. The cyanoketenate is a very useful unsaturated building block containing N, C and O atoms that can now be explored with relative ease and will undoubtedly unlock more interesting reactivity.

AB - Cyanoketene is a fundamental molecule that is actively being searched for in the interstellar medium. Its deprotonated form (cyanoketenate) is a heterocumulene that is isoelectronic to carbon suboxide whose structure has been the subject of debate. However, the investigation of cyanoketene and its derivatives is hampered by the lack of practical synthetic routes to these compounds. We report the first synthesis of the cyanoketenate anion in [K(18‐crown‐6)][NCCCO] (1) as a stable molecule on a multigram scale in excellent yields (>90 %). The structure of this molecule is probed crystallographically and computationally. We also explore the protonation of 1, and its reaction with triphenylsilylchloride and carbon dioxide. In all cases, anionic dimers are formed. The cyanoketene could be synthesized and crystallographically characterized when stabilized by a N‐heterocyclic carbene. The cyanoketenate is a very useful unsaturated building block containing N, C and O atoms that can now be explored with relative ease and will undoubtedly unlock more interesting reactivity.

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KW - N-heterocyclic carbene

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KW - cumulenes

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JF - Angewandte Chemie (International Edition)

M1 - e202402728

ER -

Synthesis and Reactivity of the [NCCCO]− Cyanoketenate Anion

Abstract

Bibliographical note

Keywords

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