{"title":"Investigating Reductive Elimination and Ligand Exchange Pathways from Homoleptic Lithium Nickelate Acetylide Complexes","authors":"Andryj M. Borys, Luca Vedani, Eva Hevia","doi":"10.1021/acs.organomet.4c00181","DOIUrl":null,"url":null,"abstract":"Alkali-metal nickelates have been shown to be key intermediates in a range of Ni-catalyzed transformations involving polar organometallics, but mechanistic studies into elementary reaction steps are limited. Herein, we assess reductive elimination pathways from homoleptic lithium nickelates, Li<sub>2</sub>Ni<sup>II</sup>(C≡C–R)<sub>4</sub>, (where R = Ph, <sup><i>t</i></sup>Bu, or SiMe<sub>3</sub>), to give 1,3-diynes. We find that the rate of reductive elimination varies depending on the R substituent (fast for R = Ph, slow for <sup><i>t</i></sup>Bu), and that the resulting Li/Ni<sup>0</sup> complex, in which the 1,3-diyne product remains coordinated, can adopt different structural motifs. For R = SiMe<sub>3</sub> derivatives, competing ligand exchange pathways have been identified and spectroscopically interrogated.","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.organomet.4c00181","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Alkali-metal nickelates have been shown to be key intermediates in a range of Ni-catalyzed transformations involving polar organometallics, but mechanistic studies into elementary reaction steps are limited. Herein, we assess reductive elimination pathways from homoleptic lithium nickelates, Li2NiII(C≡C–R)4, (where R = Ph, tBu, or SiMe3), to give 1,3-diynes. We find that the rate of reductive elimination varies depending on the R substituent (fast for R = Ph, slow for tBu), and that the resulting Li/Ni0 complex, in which the 1,3-diyne product remains coordinated, can adopt different structural motifs. For R = SiMe3 derivatives, competing ligand exchange pathways have been identified and spectroscopically interrogated.
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.