Activation and Reactivity of Vinylcyclobutane with Phosphine Nickel Catalysts

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2025-04-09 DOI:10.1021/acscatal.5c00920

Cherish Nie, Chloe Park, Junho Kim, Paul J. Chirik

{"title":"Activation and Reactivity of Vinylcyclobutane with Phosphine Nickel Catalysts","authors":"Cherish Nie, Chloe Park, Junho Kim, Paul J. Chirik","doi":"10.1021/acscatal.5c00920","DOIUrl":null,"url":null,"abstract":"A series of monodentate phosphine ligands was evaluated for the nickel-mediated activation of vinylcyclobutane (VCB) by oxidative addition to form the corresponding η1,η3-metallacycles. The addition of VCB to equimolar mixtures of phosphine and Ni(COD)2 (COD = 1,5-cyclooctadiene) produced a mixture of P2Ni(COD), P2Ni(VCB), and/or P1Ni(VCB)2. The accessibility of a VCB-derived P1Ni(II) alkyl,allyl-metallacycle correlated with an increasing number of alkyl substituents on the phosphine. Among trialkyl phosphines, PCy3 and PiPr3 were the most effective for metallacycle formation. The VCB-derived metallacycles (Cy3P)Ni(C6H10) and (iPr3P)Ni(C6H10) were isolated and characterized by NMR spectroscopy and single-crystal X-ray diffraction. The thermal and photochemical reactivity of (Cy3P)Ni(C6H10) was explored and compared to related (NHC)Ni(C6H10) metallacycles (NHC = N-heterocyclic carbene). Catalytic VCB-activation was observed with (Cy3P)Ni(C6H10) at 120 °C and furnished products from retro-[2 + 2] cycloaddition – ethylene, vinylcyclohexene, and cyclooctadiene – as well as 2,4-hexadiene arising from β-H elimination. Catalytic activation of VCB was observed upon irradiation of (Cy3P)Ni(C6H10) with blue light at 60 °C with improved selectivity for retro-[2 + 2] products over β-Η elimination and [2 + 1] cycloaddition products compared to NHC analogues. (Cy3P)Ni(C6H10) was also found to catalyze the retro-[2 + 2] depolymerization of (1,n′-divinyl)oligocyclobutane, but the presence of substituents on the cyclobutane ring resulted in an increased preference for β-H elimination.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":13.1000,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.5c00920","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

Abstract

A series of monodentate phosphine ligands was evaluated for the nickel-mediated activation of vinylcyclobutane (VCB) by oxidative addition to form the corresponding η¹,η³-metallacycles. The addition of VCB to equimolar mixtures of phosphine and Ni(COD)₂ (COD = 1,5-cyclooctadiene) produced a mixture of P₂Ni(COD), P₂Ni(VCB), and/or P₁Ni(VCB)₂. The accessibility of a VCB-derived P₁Ni(II) alkyl,allyl-metallacycle correlated with an increasing number of alkyl substituents on the phosphine. Among trialkyl phosphines, PCy₃ and PⁱPr₃ were the most effective for metallacycle formation. The VCB-derived metallacycles (Cy₃P)Ni(C₆H₁₀) and (ⁱPr₃P)Ni(C₆H₁₀) were isolated and characterized by NMR spectroscopy and single-crystal X-ray diffraction. The thermal and photochemical reactivity of (Cy₃P)Ni(C₆H₁₀) was explored and compared to related (NHC)Ni(C₆H₁₀) metallacycles (NHC = N-heterocyclic carbene). Catalytic VCB-activation was observed with (Cy₃P)Ni(C₆H₁₀) at 120 °C and furnished products from retro-[2 + 2] cycloaddition – ethylene, vinylcyclohexene, and cyclooctadiene – as well as 2,4-hexadiene arising from β-H elimination. Catalytic activation of VCB was observed upon irradiation of (Cy₃P)Ni(C₆H₁₀) with blue light at 60 °C with improved selectivity for retro-[2 + 2] products over β-Η elimination and [2 + 1] cycloaddition products compared to NHC analogues. (Cy₃P)Ni(C₆H₁₀) was also found to catalyze the retro-[2 + 2] depolymerization of (1,n′-divinyl)oligocyclobutane, but the presence of substituents on the cyclobutane ring resulted in an increased preference for β-H elimination.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

乙烯基环丁烷在膦镍催化剂上的活化及反应性

研究了一系列单齿膦配体在镍介导的乙烯基环丁烷（VCB）氧化加成反应中形成相应的η - 1，η - 3金属环的活性。将VCB加入到膦和Ni(COD)2 （COD = 1,5-环二烯）的等摩尔混合物中，产生P2Ni(COD), P2Ni（VCB）和/或P1Ni(VCB)2的混合物。vcb衍生的P1Ni（II）烷基、烯丙基金属环的可及性与磷化氢上烷基取代基数量的增加有关。在三烷基膦中，PCy3和PiPr3对金属环的形成最有效。分离得到了vcb衍生金属环（Cy3P）Ni（C6H10）和（iPr3P）Ni(C6H10)，并用核磁共振波谱和单晶x射线衍射对其进行了表征。考察了（Cy3P）Ni（C6H10）金属环（NHC = n -杂环碳）的热光化学反应性，并与相关的（NHC）Ni（C6H10）金属环（NHC = n -杂环碳）进行了比较。在120℃下，用（Cy3P）Ni（C6H10）催化vcb活化，得到了由[2 + 2]环加成-乙烯、乙烯基环己烯、环二烯和β-H消除产生的2,4-己二烯的产物。在60°C蓝光照射（Cy3P）Ni（C6H10）时观察到VCB的催化活化，与NHC类似物相比，还原-[2 + 2]产物比β-Η消除产物和[2 + 1]环加成产物的选择性更高。（Cy3P）Ni（C6H10）也可以催化（1,n ' -二乙烯基）低聚环丁烷的逆向[2 + 2]解聚，但环丁烷环上取代基的存在导致β-H消除的偏好增加。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.