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Letter. On the activation of [CrCl3{R-SN(H)S-R}] catalysts for selective trimerization of ethene: a freeze-quench Cr K-edge XAFS study

Letter. On the activation of [CrCl3{R-SN(H)S-R}] catalysts for selective trimerization of ethene: a freeze-quench Cr K-edge XAFS study
Letter. On the activation of [CrCl3{R-SN(H)S-R}] catalysts for selective trimerization of ethene: a freeze-quench Cr K-edge XAFS study
Homogeneous chromium catalysts for the selective conversion of ethene to hex-1-ene are formed from Cr(III) reagents, amino-thioether ligands of the type HN(CH2CH2SR)2, and aluminum reagents. In this study the early activation steps are investigated by EPR, UV-visible and Cr K-edge XAFS spectroscopy; rapid stopped-flow mixing and a freeze-quench allows good quality EXAFS analysis of a species formed in ~ 1 second of reaction. This is shown to involve reduction to Cr(II) and deprotonation of a NH group of the auxiliary ligand. This 4-coordinate metal-center may act as precursor for the coordination of ethene and subsequent selective oligomerization.
homogeneous catalysis, chromium, oligomerization, XAFS spectroscopy, DFT calculations
2155-5435
4201-4204
Bartlett, Stuart A.
1adeb675-9e04-4635-bdb8-df3833333f34
Moulin, Jerome
568937e0-1a00-4347-9368-7ac2b13c1869
Tromp, Moniek
a5da2bdf-9f4e-452a-8aa8-032e0c9b6660
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Dent, Andrew J.
24c2a218-cb0e-4193-af0b-3ff1dc42b552
Cibin, Giannantonio
61a833d3-097f-4817-bcd3-6b26cf42dbe5
McGuinness, David S.
8b93fc01-6b9c-4d5b-b77b-6e992a783bde
Evans, John
05890433-0155-49fe-a65d-38c90ea25c69
Bartlett, Stuart A.
1adeb675-9e04-4635-bdb8-df3833333f34
Moulin, Jerome
568937e0-1a00-4347-9368-7ac2b13c1869
Tromp, Moniek
a5da2bdf-9f4e-452a-8aa8-032e0c9b6660
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Dent, Andrew J.
24c2a218-cb0e-4193-af0b-3ff1dc42b552
Cibin, Giannantonio
61a833d3-097f-4817-bcd3-6b26cf42dbe5
McGuinness, David S.
8b93fc01-6b9c-4d5b-b77b-6e992a783bde
Evans, John
05890433-0155-49fe-a65d-38c90ea25c69

Bartlett, Stuart A., Moulin, Jerome, Tromp, Moniek, Reid, Gillian, Dent, Andrew J., Cibin, Giannantonio, McGuinness, David S. and Evans, John (2014) Letter. On the activation of [CrCl3{R-SN(H)S-R}] catalysts for selective trimerization of ethene: a freeze-quench Cr K-edge XAFS study. ACS Catalysis, 4201-4204. (doi:10.1021/cs501017g).

Record type: Article

Abstract

Homogeneous chromium catalysts for the selective conversion of ethene to hex-1-ene are formed from Cr(III) reagents, amino-thioether ligands of the type HN(CH2CH2SR)2, and aluminum reagents. In this study the early activation steps are investigated by EPR, UV-visible and Cr K-edge XAFS spectroscopy; rapid stopped-flow mixing and a freeze-quench allows good quality EXAFS analysis of a species formed in ~ 1 second of reaction. This is shown to involve reduction to Cr(II) and deprotonation of a NH group of the auxiliary ligand. This 4-coordinate metal-center may act as precursor for the coordination of ethene and subsequent selective oligomerization.

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cs501017g - Accepted Manuscript
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Published date: 21 October 2014
Keywords: homogeneous catalysis, chromium, oligomerization, XAFS spectroscopy, DFT calculations
Organisations: Chemistry

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Local EPrints ID: 370458
URI: http://eprints.soton.ac.uk/id/eprint/370458
ISSN: 2155-5435
PURE UUID: cbdf26b1-d150-4617-b8bd-ebda284fb78b
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 24 Oct 2014 15:33
Last modified: 07 Oct 2020 01:36

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Contributors

Author: Stuart A. Bartlett
Author: Jerome Moulin
Author: Moniek Tromp
Author: Gillian Reid ORCID iD
Author: Andrew J. Dent
Author: Giannantonio Cibin
Author: David S. McGuinness
Author: John Evans

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