Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior
The famous metallacycle mechanism for ethylene tetramerization has received serious attention in recent decades, as the possibility of further ring expansion may not ensure the specific formation of 1-octene. However, there are limited discussions available on a precise understanding of the ethylene...
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2025
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| _version_ | 1852020484136239104 |
|---|---|
| author | Jiale Peng (20099928) |
| author2 | Long Chen (315739) Mengyu Zhu (2848586) Li Sun (4624) Zuoxiang Zeng (2606638) Zhen Liu (74646) |
| author2_role | author author author author author |
| author_facet | Jiale Peng (20099928) Long Chen (315739) Mengyu Zhu (2848586) Li Sun (4624) Zuoxiang Zeng (2606638) Zhen Liu (74646) |
| author_role | author |
| dc.creator.none.fl_str_mv | Jiale Peng (20099928) Long Chen (315739) Mengyu Zhu (2848586) Li Sun (4624) Zuoxiang Zeng (2606638) Zhen Liu (74646) |
| dc.date.none.fl_str_mv | 2025-05-13T20:47:40Z |
| dc.identifier.none.fl_str_mv | 10.1021/acscatal.5c02037.s002 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/dataset/Overcoming_Conformational_Complexity_to_Elucidate_Selective_Ethylene_Tetramerization_Behavior/29053677 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biophysics Biochemistry Biotechnology Sociology Space Science Environmental Sciences not elsewhere classified Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified received serious attention limited discussions available highly flexible nine geometric constraint resulting famous metallacycle mechanism extended metallacycle pathway even high molecular computational results demonstrated next ethylene insertion weight polyethylene via ethylene tetramerization behavior overcoming conformational complexity ring expansion may ethylene tetramerization conformational complexity ring expansion membered ring unique boat specific formation selective formation recent decades rapidly eliminate precise understanding pnp complex octene via metallacycles plays mechanistic studies less likely key role higher oligomer elimination step defined cr chair form better understanding also highlights |
| dc.title.none.fl_str_mv | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior |
| dc.type.none.fl_str_mv | Dataset info:eu-repo/semantics/publishedVersion dataset |
| description | The famous metallacycle mechanism for ethylene tetramerization has received serious attention in recent decades, as the possibility of further ring expansion may not ensure the specific formation of 1-octene. However, there are limited discussions available on a precise understanding of the ethylene tetramerization behavior. Herein, a detailed density functional theory investigation was performed to explore continuous metallacyclic chain growth. Based on the well-defined Cr/PNP complex, computational results demonstrated that the flexibility of metallacycles plays a key role in controlling the ring expansion. A careful conformational search revealed that prior to the next ethylene insertion, the highly flexible nine-membered ring can rapidly eliminate to 1-octene via the 3,9-H shift transition state, which adopts a unique boat-chair form to afford minimal nonbonded repulsion, while a geometric constraint resulting from the β-H agostic interaction balances the ethylene migratory insertion step, which diminished the impact of ring flexibility. As a result, the selective formation of 1-octene can be expected, while the production of higher oligomer or even high molecular-weight polyethylene via the extended metallacycle pathway is less likely to occur. The expansion of conformationally flexible metallacycles may promote the H-elimination step, which indicated that continuous metallacyclic chain growth is hindered in operation. This study not only contributes to a better understanding of the diverse modes regarding ethylene conversion but also highlights the impact of conformational complexity on mechanistic studies. |
| eu_rights_str_mv | openAccess |
| id | Manara_8014d85f1a2cb3fa2b880e1fa8ce8a8d |
| identifier_str_mv | 10.1021/acscatal.5c02037.s002 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/29053677 |
| publishDate | 2025 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY-NC 4.0 |
| spelling | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization BehaviorJiale Peng (20099928)Long Chen (315739)Mengyu Zhu (2848586)Li Sun (4624)Zuoxiang Zeng (2606638)Zhen Liu (74646)BiophysicsBiochemistryBiotechnologySociologySpace ScienceEnvironmental Sciences not elsewhere classifiedBiological Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedreceived serious attentionlimited discussions availablehighly flexible ninegeometric constraint resultingfamous metallacycle mechanismextended metallacycle pathwayeven high molecularcomputational results demonstratednext ethylene insertionweight polyethylene viaethylene tetramerization behaviorovercoming conformational complexityring expansion mayethylene tetramerizationconformational complexityring expansionmembered ringunique boatspecific formationselective formationrecent decadesrapidly eliminateprecise understandingpnp complexoctene viametallacycles playsmechanistic studiesless likelykey rolehigher oligomerelimination stepdefined crchair formbetter understandingalso highlightsThe famous metallacycle mechanism for ethylene tetramerization has received serious attention in recent decades, as the possibility of further ring expansion may not ensure the specific formation of 1-octene. However, there are limited discussions available on a precise understanding of the ethylene tetramerization behavior. Herein, a detailed density functional theory investigation was performed to explore continuous metallacyclic chain growth. Based on the well-defined Cr/PNP complex, computational results demonstrated that the flexibility of metallacycles plays a key role in controlling the ring expansion. A careful conformational search revealed that prior to the next ethylene insertion, the highly flexible nine-membered ring can rapidly eliminate to 1-octene via the 3,9-H shift transition state, which adopts a unique boat-chair form to afford minimal nonbonded repulsion, while a geometric constraint resulting from the β-H agostic interaction balances the ethylene migratory insertion step, which diminished the impact of ring flexibility. As a result, the selective formation of 1-octene can be expected, while the production of higher oligomer or even high molecular-weight polyethylene via the extended metallacycle pathway is less likely to occur. The expansion of conformationally flexible metallacycles may promote the H-elimination step, which indicated that continuous metallacyclic chain growth is hindered in operation. This study not only contributes to a better understanding of the diverse modes regarding ethylene conversion but also highlights the impact of conformational complexity on mechanistic studies.2025-05-13T20:47:40ZDatasetinfo:eu-repo/semantics/publishedVersiondataset10.1021/acscatal.5c02037.s002https://figshare.com/articles/dataset/Overcoming_Conformational_Complexity_to_Elucidate_Selective_Ethylene_Tetramerization_Behavior/29053677CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/290536772025-05-13T20:47:40Z |
| spellingShingle | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior Jiale Peng (20099928) Biophysics Biochemistry Biotechnology Sociology Space Science Environmental Sciences not elsewhere classified Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified received serious attention limited discussions available highly flexible nine geometric constraint resulting famous metallacycle mechanism extended metallacycle pathway even high molecular computational results demonstrated next ethylene insertion weight polyethylene via ethylene tetramerization behavior overcoming conformational complexity ring expansion may ethylene tetramerization conformational complexity ring expansion membered ring unique boat specific formation selective formation recent decades rapidly eliminate precise understanding pnp complex octene via metallacycles plays mechanistic studies less likely key role higher oligomer elimination step defined cr chair form better understanding also highlights |
| status_str | publishedVersion |
| title | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior |
| title_full | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior |
| title_fullStr | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior |
| title_full_unstemmed | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior |
| title_short | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior |
| title_sort | Overcoming Conformational Complexity to Elucidate Selective Ethylene Tetramerization Behavior |
| topic | Biophysics Biochemistry Biotechnology Sociology Space Science Environmental Sciences not elsewhere classified Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified received serious attention limited discussions available highly flexible nine geometric constraint resulting famous metallacycle mechanism extended metallacycle pathway even high molecular computational results demonstrated next ethylene insertion weight polyethylene via ethylene tetramerization behavior overcoming conformational complexity ring expansion may ethylene tetramerization conformational complexity ring expansion membered ring unique boat specific formation selective formation recent decades rapidly eliminate precise understanding pnp complex octene via metallacycles plays mechanistic studies less likely key role higher oligomer elimination step defined cr chair form better understanding also highlights |