A rational approach towards selective ethylene oligomerization via PNP-ligand design with an N-triptycene functionality

Samir Barman; E. A. Jaseer; Nestor Garcia; Mohamed Elanany; Motaz Khawaji; Wei Xu; Sibo Lin; Hassan Alasiri; Muhammad Naseem Akhtar; Rajesh Theravalappil

doi:10.1039/d2cc02456j

A rational approach towards selective ethylene oligomerization via PNP-ligand design with an N-triptycene functionality

Samir Barman^*, E. A. Jaseer^*, Nestor Garcia, Mohamed Elanany, Motaz Khawaji, Wei Xu, Sibo Lin, Hassan Alasiri, Muhammad Naseem Akhtar, Rajesh Theravalappil

^*Corresponding author for this work

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

15 Scopus citations

Abstract

Novel PNP ligands bearing an N-triptycene backbone were developed and evaluated for selective ethylene oligomerization. Upon activation with MMAO-3A, the pre-catalyst mixture containing Cr(acac)₃/ligand efficiently promotes ethylene tetramerization with remarkably high productivities (up to 1733 kg g_Cr⁻¹ h⁻¹) and C₈ olefin selectivities (up to 74.1 wt%). More importantly, ligands with a PNP moiety connecting at the 1- or 1,4-position of the triptycene molecule could achieve exceptionally high alpha (1-C₆ + 1-C₈) selectivities, exceeding 90 wt%, as a result of high 1-C₆ purity (>90 wt%) in the C₆ fraction. Based on comparative catalytic studies employing various PNP ligands with or without an N-triptycene backbone, we illustrate the fact that a rational design of PNP ligands with an optimum degree of steric profile around the N-center could provide C₆ cyclics controlled highly α-selective ethylene oligomerization.

Original language	English
Pages (from-to)	10044-10047
Number of pages	4
Journal	Chemical Communications
Volume	58
Issue number	72
DOIs	https://doi.org/10.1039/d2cc02456j
State	Published - 12 Aug 2022

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Publisher Copyright:
© 2022 The Royal Society of Chemistry.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Metals and Alloys
Materials Chemistry
Surfaces, Coatings and Films
General Chemistry
Catalysis

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title = "A rational approach towards selective ethylene oligomerization via PNP-ligand design with an N-triptycene functionality",

abstract = "Novel PNP ligands bearing an N-triptycene backbone were developed and evaluated for selective ethylene oligomerization. Upon activation with MMAO-3A, the pre-catalyst mixture containing Cr(acac)3/ligand efficiently promotes ethylene tetramerization with remarkably high productivities (up to 1733 kg gCr−1 h−1) and C8 olefin selectivities (up to 74.1 wt%). More importantly, ligands with a PNP moiety connecting at the 1- or 1,4-position of the triptycene molecule could achieve exceptionally high alpha (1-C6 + 1-C8) selectivities, exceeding 90 wt%, as a result of high 1-C6 purity (>90 wt%) in the C6 fraction. Based on comparative catalytic studies employing various PNP ligands with or without an N-triptycene backbone, we illustrate the fact that a rational design of PNP ligands with an optimum degree of steric profile around the N-center could provide C6 cyclics controlled highly α-selective ethylene oligomerization.",

author = "Samir Barman and Jaseer, {E. A.} and Nestor Garcia and Mohamed Elanany and Motaz Khawaji and Wei Xu and Sibo Lin and Hassan Alasiri and Akhtar, {Muhammad Naseem} and Rajesh Theravalappil",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = aug,

day = "12",

doi = "10.1039/d2cc02456j",

language = "English",

volume = "58",

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T1 - A rational approach towards selective ethylene oligomerization via PNP-ligand design with an N-triptycene functionality

AU - Barman, Samir

AU - Jaseer, E. A.

AU - Garcia, Nestor

AU - Elanany, Mohamed

AU - Khawaji, Motaz

AU - Xu, Wei

AU - Lin, Sibo

AU - Alasiri, Hassan

AU - Akhtar, Muhammad Naseem

AU - Theravalappil, Rajesh

PY - 2022/8/12

Y1 - 2022/8/12

N2 - Novel PNP ligands bearing an N-triptycene backbone were developed and evaluated for selective ethylene oligomerization. Upon activation with MMAO-3A, the pre-catalyst mixture containing Cr(acac)3/ligand efficiently promotes ethylene tetramerization with remarkably high productivities (up to 1733 kg gCr−1 h−1) and C8 olefin selectivities (up to 74.1 wt%). More importantly, ligands with a PNP moiety connecting at the 1- or 1,4-position of the triptycene molecule could achieve exceptionally high alpha (1-C6 + 1-C8) selectivities, exceeding 90 wt%, as a result of high 1-C6 purity (>90 wt%) in the C6 fraction. Based on comparative catalytic studies employing various PNP ligands with or without an N-triptycene backbone, we illustrate the fact that a rational design of PNP ligands with an optimum degree of steric profile around the N-center could provide C6 cyclics controlled highly α-selective ethylene oligomerization.

AB - Novel PNP ligands bearing an N-triptycene backbone were developed and evaluated for selective ethylene oligomerization. Upon activation with MMAO-3A, the pre-catalyst mixture containing Cr(acac)3/ligand efficiently promotes ethylene tetramerization with remarkably high productivities (up to 1733 kg gCr−1 h−1) and C8 olefin selectivities (up to 74.1 wt%). More importantly, ligands with a PNP moiety connecting at the 1- or 1,4-position of the triptycene molecule could achieve exceptionally high alpha (1-C6 + 1-C8) selectivities, exceeding 90 wt%, as a result of high 1-C6 purity (>90 wt%) in the C6 fraction. Based on comparative catalytic studies employing various PNP ligands with or without an N-triptycene backbone, we illustrate the fact that a rational design of PNP ligands with an optimum degree of steric profile around the N-center could provide C6 cyclics controlled highly α-selective ethylene oligomerization.

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U2 - 10.1039/d2cc02456j

DO - 10.1039/d2cc02456j

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AN - SCOPUS:85136622696

SN - 1359-7345

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JO - Chemical Communications

JF - Chemical Communications

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ER -

A rational approach towards selective ethylene oligomerization via PNP-ligand design with an N-triptycene functionality

Abstract

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ASJC Scopus subject areas

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