期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 51, 页码 26518-26522出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202111389
关键词
cyclopropanation; metallacycles; metathesis; nickel; pincer compounds
资金
- European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program [715060]
- Netherlands Organization for Scientific Research (NWO)
- SURF Foundation
- European Research Council (ERC) [715060] Funding Source: European Research Council (ERC)
Nickelacyclobutanes are reactive intermediates in the reaction of nickel carbenes and olefins, which can selectively decompose into cyclopropanes, metathesis, or beta-hydride elimination pathways depending on the coordination of different coligands. DFT calculations provide insight into the mechanisms of these pathways.
Nickelacyclobutanes are mostly invoked as reactive intermediates in the reaction of nickel carbenes and olefins to yield cyclopropanes. Nevertheless, early work suggested that other decomposition routes such as beta-hydride elimination and even metathesis could be accessible. Herein, we report the isolation and characterization of a stable pentacoordinated nickelacyclobutane incorporated in a pincer complex. The coordination of different coligands to the nickelacyclobutane determines its selective decomposition along cyclopropanation, metathesis or apparent beta-hydride elimination pathways. DFT calculations shed light on the mechanism of these different pathways.
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