Metathetic Oxidation of 2-Butenes to Acetaldehyde by Molecular Oxygen Using the Single-Site Olefin Metathesis Catalyst (≡SiO)2Mo(=O)2

Frédéric Le Quéméner; Samir Barman; Nicolas Merle; Maha A. Aljuhani; Manoja K. Samantaray; Youssef Saih; Kai C. Szeto; Aimery De Mallmann; Yury Minenkov; Kuo Wei Huang; Luigi Cavallo; Mostafa Taoufik; Jean Marie Basset

doi:10.1021/acscatal.8b01767

Metathetic Oxidation of 2-Butenes to Acetaldehyde by Molecular Oxygen Using the Single-Site Olefin Metathesis Catalyst (≡SiO)₂Mo(=O)₂

Frédéric Le Quéméner, Samir Barman, Nicolas Merle, Maha A. Aljuhani, Manoja K. Samantaray, Youssef Saih, Kai C. Szeto, Aimery De Mallmann, Yury Minenkov, Kuo Wei Huang^*, Luigi Cavallo, Mostafa Taoufik, Jean Marie Basset

^*Corresponding author for this work

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

18 Scopus citations

Abstract

The catalytic oxidation of cis-2-butene and propylene with molecular oxygen in the presence of a well-defined surface coordination compound, (≡SiO)₂Mo(=O)₂, affords acetaldehyde. Using a cis-2-butene/O₂ feed at 350-400 °C, the reaction yields a conversion of approximately 10% and an acetaldehyde selectivity of approximately 70%. This performance is maintained up to an experimental time of 20 h in a continuous flow reactor. The Mo(bis-oxo) surface compound was fully characterized by multiple spectroscopic techniques as well as surface microanalysis. The results from quantum mechanics calculations indicate that the reaction proceeds via [2 + 2] cycloaddition/cycloelimination steps with the formation of metalla-oxacyclobutane intermediates, analogous to the Chauvin mechanism in olefin metathesis.

Original language	English (US)
Pages (from-to)	7549-7555
Number of pages	7
Journal	ACS Catalysis
Volume	8
Issue number	8
DOIs	https://doi.org/10.1021/acscatal.8b01767
State	Published - Aug 3 2018

Bibliographical note

Funding Information:
The Competitive Research Grant Program, supported by the KAUST Research Fund (project # 2174 CGR3) is gratefully acknowledged for financial support. We wish to thank Olivier Mathon for his help during the recording of the XAS spectra on BM23 beamline at ESRF (experiment code IN-986). For computer time, this study employed the resources of the KAUST Supercomputing Laboratory (KSL).

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1021/acscatal.8b01767

Cite this

Le Quéméner, F., Barman, S., Merle, N., Aljuhani, M. A., Samantaray, M. K., Saih, Y., Szeto, K. C., De Mallmann, A., Minenkov, Y., Huang, K. W., Cavallo, L., Taoufik, M., & Basset, J. M. (2018). Metathetic Oxidation of 2-Butenes to Acetaldehyde by Molecular Oxygen Using the Single-Site Olefin Metathesis Catalyst (≡SiO)₂Mo(=O)₂ ACS Catalysis, 8(8), 7549-7555. https://doi.org/10.1021/acscatal.8b01767

@article{6094ec4f23e049faba646be816a68a51,

title = "Metathetic Oxidation of 2-Butenes to Acetaldehyde by Molecular Oxygen Using the Single-Site Olefin Metathesis Catalyst (≡SiO)2Mo(=O)2 ",

abstract = "The catalytic oxidation of cis-2-butene and propylene with molecular oxygen in the presence of a well-defined surface coordination compound, (≡SiO)2Mo(=O)2, affords acetaldehyde. Using a cis-2-butene/O2 feed at 350-400 °C, the reaction yields a conversion of approximately 10% and an acetaldehyde selectivity of approximately 70%. This performance is maintained up to an experimental time of 20 h in a continuous flow reactor. The Mo(bis-oxo) surface compound was fully characterized by multiple spectroscopic techniques as well as surface microanalysis. The results from quantum mechanics calculations indicate that the reaction proceeds via [2 + 2] cycloaddition/cycloelimination steps with the formation of metalla-oxacyclobutane intermediates, analogous to the Chauvin mechanism in olefin metathesis.",

author = "{Le Qu{\'e}m{\'e}ner}, Fr{\'e}d{\'e}ric and Samir Barman and Nicolas Merle and Aljuhani, {Maha A.} and Samantaray, {Manoja K.} and Youssef Saih and Szeto, {Kai C.} and {De Mallmann}, Aimery and Yury Minenkov and Huang, {Kuo Wei} and Luigi Cavallo and Mostafa Taoufik and Basset, {Jean Marie}",

note = "Funding Information: The Competitive Research Grant Program, supported by the KAUST Research Fund (project # 2174 CGR3) is gratefully acknowledged for financial support. We wish to thank Olivier Mathon for his help during the recording of the XAS spectra on BM23 beamline at ESRF (experiment code IN-986). For computer time, this study employed the resources of the KAUST Supercomputing Laboratory (KSL). Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = aug,

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doi = "10.1021/acscatal.8b01767",

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Le Quéméner, F, Barman, S, Merle, N, Aljuhani, MA , Samantaray, MK , Saih, Y, Szeto, KC, De Mallmann, A, Minenkov, Y, Huang, KW , Cavallo, L, Taoufik, M & Basset, JM 2018, 'Metathetic Oxidation of 2-Butenes to Acetaldehyde by Molecular Oxygen Using the Single-Site Olefin Metathesis Catalyst (≡SiO)₂Mo(=O)₂ ', ACS Catalysis, vol. 8, no. 8, pp. 7549-7555. https://doi.org/10.1021/acscatal.8b01767

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AU - Le Quéméner, Frédéric

AU - Barman, Samir

AU - Merle, Nicolas

AU - Aljuhani, Maha A.

AU - Samantaray, Manoja K.

AU - Saih, Youssef

AU - Szeto, Kai C.

AU - De Mallmann, Aimery

AU - Minenkov, Yury

AU - Huang, Kuo Wei

AU - Cavallo, Luigi

AU - Taoufik, Mostafa

AU - Basset, Jean Marie

N1 - Funding Information: The Competitive Research Grant Program, supported by the KAUST Research Fund (project # 2174 CGR3) is gratefully acknowledged for financial support. We wish to thank Olivier Mathon for his help during the recording of the XAS spectra on BM23 beamline at ESRF (experiment code IN-986). For computer time, this study employed the resources of the KAUST Supercomputing Laboratory (KSL). Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/8/3

Y1 - 2018/8/3

N2 - The catalytic oxidation of cis-2-butene and propylene with molecular oxygen in the presence of a well-defined surface coordination compound, (≡SiO)2Mo(=O)2, affords acetaldehyde. Using a cis-2-butene/O2 feed at 350-400 °C, the reaction yields a conversion of approximately 10% and an acetaldehyde selectivity of approximately 70%. This performance is maintained up to an experimental time of 20 h in a continuous flow reactor. The Mo(bis-oxo) surface compound was fully characterized by multiple spectroscopic techniques as well as surface microanalysis. The results from quantum mechanics calculations indicate that the reaction proceeds via [2 + 2] cycloaddition/cycloelimination steps with the formation of metalla-oxacyclobutane intermediates, analogous to the Chauvin mechanism in olefin metathesis.

AB - The catalytic oxidation of cis-2-butene and propylene with molecular oxygen in the presence of a well-defined surface coordination compound, (≡SiO)2Mo(=O)2, affords acetaldehyde. Using a cis-2-butene/O2 feed at 350-400 °C, the reaction yields a conversion of approximately 10% and an acetaldehyde selectivity of approximately 70%. This performance is maintained up to an experimental time of 20 h in a continuous flow reactor. The Mo(bis-oxo) surface compound was fully characterized by multiple spectroscopic techniques as well as surface microanalysis. The results from quantum mechanics calculations indicate that the reaction proceeds via [2 + 2] cycloaddition/cycloelimination steps with the formation of metalla-oxacyclobutane intermediates, analogous to the Chauvin mechanism in olefin metathesis.

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