Shirley Hernandez, Dmitry S. Belov, Vasilisa Krivovicheva, Shuruthi Senthil and Konstantin V. Bukhryakov*,
{"title":"Decreasing the Bond Order between Vanadium and Oxo Ligand to Form 3d Schrock Carbynes","authors":"Shirley Hernandez, Dmitry S. Belov, Vasilisa Krivovicheva, Shuruthi Senthil and Konstantin V. Bukhryakov*, ","doi":"10.1021/jacs.4c07588","DOIUrl":null,"url":null,"abstract":"<p >Preserving vanadium in a high oxidation state during chemical transformations can be challenging due to the oxidizing nature of V(+5) species. Oxo and similar isoelectronic ligands have been utilized to stabilize V(+5) by extensive π-donation. However, decreasing the bond order between V and the oxo ligand often results in a reduction of the metal center. Herein, we report a unique transformation involving anionic V(+5) alkylidene that converts a V(+5) oxo complex to a V(+5) alkylidyne in three steps without altering the oxidation state of the metal center. This method has been used to obtain rare 3d Schrock carbynes, which provide easy and scalable access to V(+5) alkylidynes.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c07588","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Preserving vanadium in a high oxidation state during chemical transformations can be challenging due to the oxidizing nature of V(+5) species. Oxo and similar isoelectronic ligands have been utilized to stabilize V(+5) by extensive π-donation. However, decreasing the bond order between V and the oxo ligand often results in a reduction of the metal center. Herein, we report a unique transformation involving anionic V(+5) alkylidene that converts a V(+5) oxo complex to a V(+5) alkylidyne in three steps without altering the oxidation state of the metal center. This method has been used to obtain rare 3d Schrock carbynes, which provide easy and scalable access to V(+5) alkylidynes.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.