John R. Rivet, Briana S. Henderson, Steve Marshall, Keosha Cade, David R. Wilson, Heather A. Spinney, Jianbo Hou and Alex J. Nett*,
{"title":"膦酰亚胺支撑的乙烯/丙烯酸酯共聚镍催化剂","authors":"John R. Rivet, Briana S. Henderson, Steve Marshall, Keosha Cade, David R. Wilson, Heather A. Spinney, Jianbo Hou and Alex J. Nett*, ","doi":"10.1021/acs.organomet.4c00034","DOIUrl":null,"url":null,"abstract":"<p >Phosphine–imidate-supported nickel catalysts were synthesized and tested for ethylene/acrylate copolymerization activity. Phosphine–amide metalation studies with (pyridine)<sub>2</sub>Ni(CH<sub>2</sub>Si(CH<sub>3</sub>)<sub>3</sub>)<sub>2</sub> (py<sub>2</sub>Ni(CH<sub>2</sub>TMS)<sub>2</sub>) suggest that the metalation proceeds via an intermediate phosphine–amide complex ([P,O–amide]Ni(CH<sub>2</sub>TMS)<sub>2</sub>). Subsequent deprotonation of the amide N–H gives access to the phosphine–imidate-supported nickel complex ([P,O–imidate]pyNi(CH<sub>2</sub>TMS)). The imidate form of the ligand proved to be critical for polymerization activity. The phosphine–imidate nickel catalysts described herein were capable of producing ethylene/acrylate copolymers with molecular weights (<i>M</i><sub>w</sub>) from 700 to 120,000 g/mol and with acrylate incorporation >2.6 mol % in some cases. It was determined that hemilabile alkoxy groups on the phosphine aryl groups were necessary to achieve high <i>M</i><sub>w</sub> and acrylate incorporation. These results demonstrate that phosphine–amides, a well-studied ligand class, can be utilized in the imidate form to access highly active neutral nickel polymerization catalysts.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Phosphine–Imidate-Supported Nickel Catalysts for Ethylene/Acrylate Copolymerization\",\"authors\":\"John R. Rivet, Briana S. Henderson, Steve Marshall, Keosha Cade, David R. Wilson, Heather A. Spinney, Jianbo Hou and Alex J. Nett*, \",\"doi\":\"10.1021/acs.organomet.4c00034\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Phosphine–imidate-supported nickel catalysts were synthesized and tested for ethylene/acrylate copolymerization activity. Phosphine–amide metalation studies with (pyridine)<sub>2</sub>Ni(CH<sub>2</sub>Si(CH<sub>3</sub>)<sub>3</sub>)<sub>2</sub> (py<sub>2</sub>Ni(CH<sub>2</sub>TMS)<sub>2</sub>) suggest that the metalation proceeds via an intermediate phosphine–amide complex ([P,O–amide]Ni(CH<sub>2</sub>TMS)<sub>2</sub>). Subsequent deprotonation of the amide N–H gives access to the phosphine–imidate-supported nickel complex ([P,O–imidate]pyNi(CH<sub>2</sub>TMS)). The imidate form of the ligand proved to be critical for polymerization activity. The phosphine–imidate nickel catalysts described herein were capable of producing ethylene/acrylate copolymers with molecular weights (<i>M</i><sub>w</sub>) from 700 to 120,000 g/mol and with acrylate incorporation >2.6 mol % in some cases. It was determined that hemilabile alkoxy groups on the phosphine aryl groups were necessary to achieve high <i>M</i><sub>w</sub> and acrylate incorporation. These results demonstrate that phosphine–amides, a well-studied ligand class, can be utilized in the imidate form to access highly active neutral nickel polymerization catalysts.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.5000,\"publicationDate\":\"2024-04-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00034\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00034","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Phosphine–Imidate-Supported Nickel Catalysts for Ethylene/Acrylate Copolymerization
Phosphine–imidate-supported nickel catalysts were synthesized and tested for ethylene/acrylate copolymerization activity. Phosphine–amide metalation studies with (pyridine)2Ni(CH2Si(CH3)3)2 (py2Ni(CH2TMS)2) suggest that the metalation proceeds via an intermediate phosphine–amide complex ([P,O–amide]Ni(CH2TMS)2). Subsequent deprotonation of the amide N–H gives access to the phosphine–imidate-supported nickel complex ([P,O–imidate]pyNi(CH2TMS)). The imidate form of the ligand proved to be critical for polymerization activity. The phosphine–imidate nickel catalysts described herein were capable of producing ethylene/acrylate copolymers with molecular weights (Mw) from 700 to 120,000 g/mol and with acrylate incorporation >2.6 mol % in some cases. It was determined that hemilabile alkoxy groups on the phosphine aryl groups were necessary to achieve high Mw and acrylate incorporation. These results demonstrate that phosphine–amides, a well-studied ligand class, can be utilized in the imidate form to access highly active neutral nickel polymerization catalysts.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.