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Jeffrey Miller
Purdue University West Lafayette
Corresponding Author
ORCiD: https://orcid.org/0000-0002-6269-0620
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In heterogeneous catalysis, olefin oligomerization is typically performed on immobilized transition metal ions, such as Ni2+ and Cr3+. Here we report that silica-supported, single site catalysts containing immobilized, main group Zn2+ and Ga3+ ions catalyze ethylene and propylene oligomerization to an equilibrium distribution of linear olefins with rates similar to that of Ni2+. The molecular weight distribution of products formed on Zn2+ is similar to Ni2+; while Ga3+ forms higher molecular weight olefins. In situ spectroscopic and computational studies suggest that oligomerization unexpectedly occurs by the Cossee-Arlman mechanism via metal hydride and metal alkyl intermediates formed during olefin insertion and β-hydride elimination elementary steps. Initiation of the catalytic cycle is proposed to occur by heterolytic C-H dissociation of ethylene, which occurs at about 250°C where oligomerization is catalytically relevant. This work reports new chemistry for main group metal catalysts with potential for development of new olefin processes.
Keywords
Silica-supported Catalysts, Cossee-Arlman Mechanism, Metal Hydride and Metal Alkyl Intermediates, Olefin Processes
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There is NO Competing Interest.
This is a list of supplementary files associated with this preprint. Click to download.
- Scheme1.png
Scheme 1. Cossee-Arlman Ni oligomerization mechanism21
- NatureCommSI1020.docx
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See the published version of this preprint at Nature Communications.
This is a preprint, a preliminary version of a manuscript that has not completed peer review at a journal. Research Square does not conduct peer review prior to posting preprints. The posting of a preprint on this server should not be interpreted as an endorsement of its validity or suitability for dissemination as established information or for guiding clinical practice.
Learn more about In Review
Article
Jeffrey Miller
Purdue University West Lafayette
Corresponding Author
ORCiD: https://orcid.org/0000-0002-6269-0620
Badges
Prescreen
This manuscript passed our Prescreen assessment
Complete author information
Appropriate declaration statements
Potential risks to human health
Prescreen
Peer Review Timeline
CURRENT STATUS: Published
View the published article at Nature Communications.
Version 1
Posted 23 Oct, 2020
Metrics
Comments: 0
PDF Downloads: ...
HTML Views: ...
Subject Areas
Catalysis
License:
This work is licensed under a CC BY 4.0 License. Read Full License
View the published article at Nature Communications.
In heterogeneous catalysis, olefin oligomerization is typically performed on immobilized transition metal ions, such as Ni2+ and Cr3+. Here we report that silica-supported, single site catalysts containing immobilized, main group Zn2+ and Ga3+ ions catalyze ethylene and propylene oligomerization to an equilibrium distribution of linear olefins with rates similar to that of Ni2+. The molecular weight distribution of products formed on Zn2+ is similar to Ni2+; while Ga3+ forms higher molecular weight olefins. In situ spectroscopic and computational studies suggest that oligomerization unexpectedly occurs by the Cossee-Arlman mechanism via metal hydride and metal alkyl intermediates formed during olefin insertion and β-hydride elimination elementary steps. Initiation of the catalytic cycle is proposed to occur by heterolytic C-H dissociation of ethylene, which occurs at about 250°C where oligomerization is catalytically relevant. This work reports new chemistry for main group metal catalysts with potential for development of new olefin processes.
Figure 1
Figure 2
Figure 3
Figure 4
There is NO Competing Interest.
This is a list of supplementary files associated with this preprint. Click to download.
- Scheme1.png
Scheme 1. Cossee-Arlman Ni oligomerization mechanism21
- NatureCommSI1020.docx
Supplementary Information
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