Highly Efficient Ethylene Tetramerization Using Cr Catalysts Constructed with Trifluoromethyl-Substituted N‑Aryl PNP Ligands

E. A. Jaseer; Nestor Garcia; Samir Barman; Motaz Khawaji; Wei Xu; Hassan Alasiri; Abdul Malik P. Peedikakkal; Muhammad Naseem Akhtar; Rajesh Theravalappil

doi:10.1021/acsomega.1c06657

Highly Efficient Ethylene Tetramerization Using Cr Catalysts Constructed with Trifluoromethyl-Substituted N‑Aryl PNP Ligands

E. A. Jaseer^*, Nestor Garcia, Samir Barman^*, Motaz Khawaji, Wei Xu, Hassan Alasiri, Abdul Malik P. Peedikakkal, Muhammad Naseem Akhtar, Rajesh Theravalappil

^*Corresponding author for this work

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

14 Scopus citations

Abstract

Tetramerization of ethylene by chromium catalysts stabilized with functionalized N-aryl phosphineamine ligands C₆H₄(m-CF₃)N(PPh₂)₂ (1), C₆H₄(p-CF₃)N(PPh₂)₂ (2), C₆H₄(o-CF₃)N=PPh₂-PPh₂ (3), and C₆H₃(3,5-bis(CF₃))N(PPh₂)₂ (4) was evaluated. The parameter optimization includes temperature, co-catalyst, and solvent. Upon activation with MMAO-3A, the new catalyst system especially with m-functional PNP ligand (1) exhibited high 1-octene selectivity and productivity while giving minimum undesirable polyethylene and C₁₀⁺ olefin by-products. Using PhCl as a solvent at 75 °C led to a remarkable α-olefin (1-C₆ + 1-C₈) selectivity (>90 wt %) at a reaction rate of 2000 kg·g_Cr⁻¹·h⁻¹. Under identical conditions, analogous PNP ligands bearing −CH₃, −Et, and −Cl functional moieties at the meta position of the N-phenyl ring displayed significantly lower reactivity. The catalyst with p-functional ligand (2) exhibited lower activity and comparable selectivities, while the Cr/PPN (with ligand 3) system gave no noticeable reactivity. The molecular structure of the precatalyst (1-Cr), exhibiting a monomeric structural feature, was elucidated with the aid of single-crystal X-ray diffraction study.

Original language	English
Pages (from-to)	16333-16340
Number of pages	8
Journal	ACS Omega
Volume	7
Issue number	19
DOIs	https://doi.org/10.1021/acsomega.1c06657
State	Published - 3 May 2022

Bibliographical note

Funding Information:
The authors would like to acknowledge the support provided by Saudi Aramco for funding project #CRP02285 at the Center for Refining and Advanced Chemicals (CRAC)/RI-KFUPM. The support of King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia, is highly appreciated.

Publisher Copyright:
© 2022 The Authors. Published by American Chemical Society.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering

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10.1021/acsomega.1c06657

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@article{a1dc65e6462f4a62a01c92071080c08a,

title = "Highly Efficient Ethylene Tetramerization Using Cr Catalysts Constructed with Trifluoromethyl-Substituted N‑Aryl PNP Ligands",

abstract = "Tetramerization of ethylene by chromium catalysts stabilized with functionalized N-aryl phosphineamine ligands C6H4(m-CF3)N(PPh2)2 (1), C6H4(p-CF3)N(PPh2)2 (2), C6H4(o-CF3)N=PPh2-PPh2 (3), and C6H3(3,5-bis(CF3))N(PPh2)2 (4) was evaluated. The parameter optimization includes temperature, co-catalyst, and solvent. Upon activation with MMAO-3A, the new catalyst system especially with m-functional PNP ligand (1) exhibited high 1-octene selectivity and productivity while giving minimum undesirable polyethylene and C10+ olefin by-products. Using PhCl as a solvent at 75 °C led to a remarkable α-olefin (1-C6 + 1-C8) selectivity (>90 wt %) at a reaction rate of 2000 kg·gCr−1·h−1. Under identical conditions, analogous PNP ligands bearing −CH3, −Et, and −Cl functional moieties at the meta position of the N-phenyl ring displayed significantly lower reactivity. The catalyst with p-functional ligand (2) exhibited lower activity and comparable selectivities, while the Cr/PPN (with ligand 3) system gave no noticeable reactivity. The molecular structure of the precatalyst (1-Cr), exhibiting a monomeric structural feature, was elucidated with the aid of single-crystal X-ray diffraction study.",

author = "Jaseer, {E. A.} and Nestor Garcia and Samir Barman and Motaz Khawaji and Wei Xu and Hassan Alasiri and Peedikakkal, {Abdul Malik P.} and Akhtar, {Muhammad Naseem} and Rajesh Theravalappil",

note = "Funding Information: The authors would like to acknowledge the support provided by Saudi Aramco for funding project #CRP02285 at the Center for Refining and Advanced Chemicals (CRAC)/RI-KFUPM. The support of King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia, is highly appreciated. Publisher Copyright: {\textcopyright} 2022 The Authors. Published by American Chemical Society.",

year = "2022",

month = may,

day = "3",

doi = "10.1021/acsomega.1c06657",

language = "English",

volume = "7",

pages = "16333--16340",

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T1 - Highly Efficient Ethylene Tetramerization Using Cr Catalysts Constructed with Trifluoromethyl-Substituted N‑Aryl PNP Ligands

AU - Jaseer, E. A.

AU - Garcia, Nestor

AU - Barman, Samir

AU - Khawaji, Motaz

AU - Xu, Wei

AU - Alasiri, Hassan

AU - Peedikakkal, Abdul Malik P.

AU - Akhtar, Muhammad Naseem

AU - Theravalappil, Rajesh

N1 - Funding Information: The authors would like to acknowledge the support provided by Saudi Aramco for funding project #CRP02285 at the Center for Refining and Advanced Chemicals (CRAC)/RI-KFUPM. The support of King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia, is highly appreciated. Publisher Copyright: © 2022 The Authors. Published by American Chemical Society.

PY - 2022/5/3

Y1 - 2022/5/3

N2 - Tetramerization of ethylene by chromium catalysts stabilized with functionalized N-aryl phosphineamine ligands C6H4(m-CF3)N(PPh2)2 (1), C6H4(p-CF3)N(PPh2)2 (2), C6H4(o-CF3)N=PPh2-PPh2 (3), and C6H3(3,5-bis(CF3))N(PPh2)2 (4) was evaluated. The parameter optimization includes temperature, co-catalyst, and solvent. Upon activation with MMAO-3A, the new catalyst system especially with m-functional PNP ligand (1) exhibited high 1-octene selectivity and productivity while giving minimum undesirable polyethylene and C10+ olefin by-products. Using PhCl as a solvent at 75 °C led to a remarkable α-olefin (1-C6 + 1-C8) selectivity (>90 wt %) at a reaction rate of 2000 kg·gCr−1·h−1. Under identical conditions, analogous PNP ligands bearing −CH3, −Et, and −Cl functional moieties at the meta position of the N-phenyl ring displayed significantly lower reactivity. The catalyst with p-functional ligand (2) exhibited lower activity and comparable selectivities, while the Cr/PPN (with ligand 3) system gave no noticeable reactivity. The molecular structure of the precatalyst (1-Cr), exhibiting a monomeric structural feature, was elucidated with the aid of single-crystal X-ray diffraction study.

AB - Tetramerization of ethylene by chromium catalysts stabilized with functionalized N-aryl phosphineamine ligands C6H4(m-CF3)N(PPh2)2 (1), C6H4(p-CF3)N(PPh2)2 (2), C6H4(o-CF3)N=PPh2-PPh2 (3), and C6H3(3,5-bis(CF3))N(PPh2)2 (4) was evaluated. The parameter optimization includes temperature, co-catalyst, and solvent. Upon activation with MMAO-3A, the new catalyst system especially with m-functional PNP ligand (1) exhibited high 1-octene selectivity and productivity while giving minimum undesirable polyethylene and C10+ olefin by-products. Using PhCl as a solvent at 75 °C led to a remarkable α-olefin (1-C6 + 1-C8) selectivity (>90 wt %) at a reaction rate of 2000 kg·gCr−1·h−1. Under identical conditions, analogous PNP ligands bearing −CH3, −Et, and −Cl functional moieties at the meta position of the N-phenyl ring displayed significantly lower reactivity. The catalyst with p-functional ligand (2) exhibited lower activity and comparable selectivities, while the Cr/PPN (with ligand 3) system gave no noticeable reactivity. The molecular structure of the precatalyst (1-Cr), exhibiting a monomeric structural feature, was elucidated with the aid of single-crystal X-ray diffraction study.

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U2 - 10.1021/acsomega.1c06657

DO - 10.1021/acsomega.1c06657

M3 - Article

AN - SCOPUS:85130047738

SN - 2470-1343

VL - 7

SP - 16333

EP - 16340

JO - ACS Omega

JF - ACS Omega

IS - 19

ER -

Highly Efficient Ethylene Tetramerization Using Cr Catalysts Constructed with Trifluoromethyl-Substituted N‑Aryl PNP Ligands

Abstract

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