First experimental evidence for a bis-ethene chromium(I) complex forming from an activated ethene oligomerization catalyst

Sonia Chabbra; D. M. Smith; Nicola Louise Bell; Allan John Bell Watson; Michael Buehl; David John Cole-Hamilton; Bela Ernest Bode

doi:10.1126/sciadv.abd7057

First experimental evidence for a bis-ethene chromium(I) complex forming from an activated ethene oligomerization catalyst

Sonia Chabbra, D. M. Smith, Nicola Louise Bell, Allan John Bell Watson, Michael Buehl, David John Cole-Hamilton, Bela Ernest Bode^*

^*Corresponding author for this work

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

Abstract

A bis-ethene chromium(I) species, which is the postulated key intermediate in the widely accepted metallacyclic mechanism for ethene oligomerization, is experimentally observed. This catalytic transformation is an important commercial route to linear α-olefins (primarily, 1-hexene and 1-octene), which act as comonomers for the production of polyethene. Here, electron paramagnetic resonance studies of a catalytic system based on [Cr(CO)₄(PNP)][Al(OC(CF₃)₃)₄] [PNP = Ph₂PN(ⁱPr)PPh₂] activated with Et₆Al₂ provide the first unequivocal evidence for a chromium(I) bis-ethene complex. The concentration of this species is enhanced under ethene and isotope labeling studies that confirm its composition as containing [Cr(C₂H₄)₂(CO)₂(PNP)]⁺. These observations open a new route to mechanistic studies of selective ethene oligomerization.

Original language	English
Article number	eabd7057
Number of pages	7
Journal	Science Advances
Volume	6
Issue number	51
DOIs	https://doi.org/10.1126/sciadv.abd7057
Publication status	Published - 18 Dec 2020

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Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution License 4.0 (CC BY). https://creativecommons.org/licenses/by/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution license, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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Bela Ernest Bode
- beb2st-andrews.acuk
Person: Academic

First experimental evidence for a bis-ethene chromium(I) complex forming from an activated ethene oligomerization catalyst (dataset)
Chabbra, S. (Creator), Smith, D. M. (Creator), Bell, N. L. (Creator), Watson, A. J. B. (Creator), Buehl, M. (Creator), Cole-Hamilton, D. J. (Creator) & Bode, B. E. (Creator), University of St Andrews, 24 Nov 2020
DOI: 10.17630/8565cf75-30d0-419f-881a-6d3c86dd0710
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title = "First experimental evidence for a bis-ethene chromium(I) complex forming from an activated ethene oligomerization catalyst",

abstract = "A bis-ethene chromium(I) species, which is the postulated key intermediate in the widely accepted metallacyclic mechanism for ethene oligomerization, is experimentally observed. This catalytic transformation is an important commercial route to linear α-olefins (primarily, 1-hexene and 1-octene), which act as comonomers for the production of polyethene. Here, electron paramagnetic resonance studies of a catalytic system based on [Cr(CO)4(PNP)][Al(OC(CF3)3)4] [PNP = Ph2PN(iPr)PPh2] activated with Et6Al2 provide the first unequivocal evidence for a chromium(I) bis-ethene complex. The concentration of this species is enhanced under ethene and isotope labeling studies that confirm its composition as containing [Cr(C2H4)2(CO)2(PNP)]+. These observations open a new route to mechanistic studies of selective ethene oligomerization.",

author = "Sonia Chabbra and Smith, {D. M.} and Bell, {Nicola Louise} and Watson, {Allan John Bell} and Michael Buehl and Cole-Hamilton, {David John} and Bode, {Bela Ernest}",

note = "Funding: This work was supported by Sasol Ltd. SC is grateful for a St Leonard{\textquoteright}s postgraduate fellowship by the University of St Andrews.",

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doi = "10.1126/sciadv.abd7057",

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T1 - First experimental evidence for a bis-ethene chromium(I) complex forming from an activated ethene oligomerization catalyst

AU - Chabbra, Sonia

AU - Smith, D. M.

AU - Bell, Nicola Louise

AU - Watson, Allan John Bell

AU - Buehl, Michael

AU - Cole-Hamilton, David John

AU - Bode, Bela Ernest

N1 - Funding: This work was supported by Sasol Ltd. SC is grateful for a St Leonard’s postgraduate fellowship by the University of St Andrews.

PY - 2020/12/18

Y1 - 2020/12/18

N2 - A bis-ethene chromium(I) species, which is the postulated key intermediate in the widely accepted metallacyclic mechanism for ethene oligomerization, is experimentally observed. This catalytic transformation is an important commercial route to linear α-olefins (primarily, 1-hexene and 1-octene), which act as comonomers for the production of polyethene. Here, electron paramagnetic resonance studies of a catalytic system based on [Cr(CO)4(PNP)][Al(OC(CF3)3)4] [PNP = Ph2PN(iPr)PPh2] activated with Et6Al2 provide the first unequivocal evidence for a chromium(I) bis-ethene complex. The concentration of this species is enhanced under ethene and isotope labeling studies that confirm its composition as containing [Cr(C2H4)2(CO)2(PNP)]+. These observations open a new route to mechanistic studies of selective ethene oligomerization.

AB - A bis-ethene chromium(I) species, which is the postulated key intermediate in the widely accepted metallacyclic mechanism for ethene oligomerization, is experimentally observed. This catalytic transformation is an important commercial route to linear α-olefins (primarily, 1-hexene and 1-octene), which act as comonomers for the production of polyethene. Here, electron paramagnetic resonance studies of a catalytic system based on [Cr(CO)4(PNP)][Al(OC(CF3)3)4] [PNP = Ph2PN(iPr)PPh2] activated with Et6Al2 provide the first unequivocal evidence for a chromium(I) bis-ethene complex. The concentration of this species is enhanced under ethene and isotope labeling studies that confirm its composition as containing [Cr(C2H4)2(CO)2(PNP)]+. These observations open a new route to mechanistic studies of selective ethene oligomerization.

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DO - 10.1126/sciadv.abd7057

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JO - Science Advances

JF - Science Advances

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M1 - eabd7057

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First experimental evidence for a bis-ethene chromium(I) complex forming from an activated ethene oligomerization catalyst

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First experimental evidence for a bis-ethene chromium(I) complex forming from an activated ethene oligomerization catalyst (dataset)

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